CN106459239B - Active energy line curing resin composition has used the hard conating laminate film and transparent resin lamilate of the resin combination - Google Patents

Active energy line curing resin composition has used the hard conating laminate film and transparent resin lamilate of the resin combination Download PDF

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CN106459239B
CN106459239B CN201580028711.2A CN201580028711A CN106459239B CN 106459239 B CN106459239 B CN 106459239B CN 201580028711 A CN201580028711 A CN 201580028711A CN 106459239 B CN106459239 B CN 106459239B
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titanium
methyl
hard conating
resin
mentioned
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CN106459239A (en
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板垣保广
伊藤茂
伊藤茂一
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Riken Technos Corp
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Riken Technos Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C08F2/00—Processes of polymerisation
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
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    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
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Abstract

The present invention relates to contain 100 mass parts of (A) multifunctional (methyl) acrylate；(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；(C) organic titanium 0.05-3 mass parts；And the active energy line curing resin composition of the particle 5-100 mass parts of (D) average grain diameter 1-300nm.Moreover, it relates to which a kind of transparent resin lamilate, has the layer of hard conating and the layer of transparent resin sheet, above-mentioned hard conating is by containing 100 mass parts of (A) multifunctional (methyl) acrylate in order since most surface layer side；(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；(C) organic titanium 0.05-3 mass parts；And the coating of the particle 5-100 mass parts of (D) average grain diameter 1-300nm is formed.

Description

Active energy line curing resin composition has used the hard painting of the resin combination Layer laminate film and transparent resin lamilate
Technical field
The present invention relates to active energy line curing resin composition and use the hard conating of the resin combination laminated Film.More particularly it relates to be capable of forming the transparency, tone, marresistance, surface hardness, flexing resistance and appearance The active energy line curing resin composition of excellent hard conating, and used the hard conating of the resin combination laminated Film.
Moreover, it relates to transparent resin lamilate.More particularly it relates to specific gravity is small, transparent, rigidity, Scoring resistance, weatherability, impact resistance and excellent in workability, and can be used as vehicle window or windshield, building window or The components such as the door and show window of the furniture such as surface element, the kitchen cabinet of families' electrical article such as door, the protection board of electronic signs, refrigerator are suitable The transparent resin lamilate that ground uses.
Background technique
In recent years, it is arranged in image display devices such as liquid crystal display, plasma scope and electroluminescent displays On, the touch panel that can be touched with finger or pen etc. while observing display to be inputted is gaining popularity.
In the past, due to requiring characteristic phase with heat resistance, dimensional stability, high transparency, high surface hardness and high rigidity etc. Unanimously, it uses in the display pannel of touch panel using glass as the article of substrate.On the other hand, glass has impact resistance Low, easy fracture；Processability is low；Processing is difficult；Specific gravity is high, very heavy；It is difficult to the curving or flexibleization requirement corresponding to display The problems such as.Therefore, it for these purposes, is being studied extensively instead of the material of glass.It proposes multiple in triacetyl cellulose The transparent tree such as element, polyethylene terephthalate, polycarbonate, polymethyl methacrylate and norbornene-based polymer The hard conating zoarium of the hard conating of surface hardness and excellent scratch resistance is formd on the surface of adipose membrane substrate (referring for example to special Sharp document 1).But marresistance is still insufficient.It needs even to be wiped repeatedly using handkerchief etc., finger can also be maintained Coating is used in the hard conating formation of the surfaces characteristic such as sliding property.
In addition, in the past due to requiring characteristic consistent with the transparency, rigidity, scoring resistance and weatherability etc., vehicle Window or components, the protection board of electronic signs and the show window such as components, the window of building or the door such as windshield etc. in use with glass Glass is the article of substrate.In addition, glass is due to its design sense with transparent feel, also extensively in the families such as refrigerator electrical article Surface element and the door of furniture such as kitchen cabinet etc. in use.On the other hand, as described above, glass has impact resistance low, easy In fracture, processability is low, specific gravity is high, very heavy the problems such as.Therefore, for these purposes, the material for replacing glass is studied extensively Material.It is laminated to propose the transparent resin with the transparent resin layers such as polycarbonate-based resin or acrylic resin and hard conating Body (referring for example to patent document 2 and 3).But scoring resistance is still insufficient.It needs even repeatedly to be scraped with rain brush etc. It smoothes out with the fingers, is repeatedly wiped with rag etc., the transparent resin lamilate of initial stage characteristic can also be maintained.
Existing technical literature
Patent document
Japanese Unexamined Patent Publication 2013-208896 bulletin
Japanese Unexamined Patent Publication 2014-043101 bulletin
Japanese Unexamined Patent Publication 2014-040017 bulletin
Summary of the invention
The technical problem to be solved by the invention
The first object of the present invention be to provide can be formed the transparency, tone, marresistance, surface hardness, flexing resistance and The active energy line curing resin composition of the excellent hard conating of surface smoothness, and provide to be used as and used the resin The image display devices such as liquid crystal display, plasma scope, the electroluminescent display of composition component (including tool Have the image display device and the not no image display device of touch panel function of touch panel function), especially touch surface The suitable hard conating laminate film of the display pannel of plate.
In addition, the second object of the present invention is to provide specific gravity small, the transparency, rigidity, scoring resistance, weatherability, resistance to punching Hitting property and excellent in workability, can be suitable for as used in the past using glass as the window of the vehicle of the article of substrate or windshield, The door and cupboard of the furniture such as surface element, the kitchen cabinet of families' electrical article such as the window or door of building, the protection board of electronic signs, refrigerator The components such as window carry out using transparent resin lamilate.
Method for solving technical problem
Present inventor has performed further investigations, as a result, it has been found that by containing multifunctional (methyl) acrylate, have it is specific The active energy ray-curable resin combination of the particle of the compound of functional group, organic titanium and the average grain diameter in particular range Object can reach above-mentioned first purpose.
In addition, the inventors discovered that by using containing multifunctional (methyl) acrylate, with the change of particular functional group The coating of the particle of object, organic titanium and the average grain diameter in particular range is closed to form transparent resin lamilate, can be reached State the second purpose.
That is, the first aspect of the present invention for reaching above-mentioned first purpose is as described below.
[1] active energy line curing resin composition contains
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts；And
(D) the particle 5-100 mass parts of average grain diameter 1-300nm.
[2] active energy line curing resin composition described in above-mentioned [1], further contains (E) hydrophobing agent 0.01-7 mass parts.
[3] active energy line curing resin composition described in above-mentioned [2], wherein above-mentioned (E) hydrophobing agent contains There is the perfluoroalkyl polyether system hydrophobing agent of (methyl) acryloyl group.
[4] hard conating laminate film, wherein at least single side in transparent resin film has by containing in above-mentioned [1]-[3] The hard conating that the coating of active energy line curing resin composition described in one is formed.
[5] hard conating laminate film has the first hard conating in order since most surface layer side；Transparent resin film layer； And second hard conating, wherein above-mentioned first hard conating is as containing active energy line curing described in any one of above-mentioned [1]-[3] The coating of property resin combination is formed.
[6] hard conating laminate film described in above-mentioned [4] or [5], wherein above-mentioned transparent resin film is poly- (methyl) propylene Imide series resin film.
[7] hard conating laminate film described in above-mentioned [6], wherein above-mentioned poly- (methyl) acrylimide resin film be by Sequence is directly laminated the first poly- (methyl) acrylimide resin (α 1)；Aromatic polycarbonate resin (β)；And The transparent multilayer film of second poly- (methyl) acrylimide resin (α 2).
[8] touch panel display panel hard conating laminate film, transparent resin film at least single side have by The hard conating that coating containing active energy line curing resin composition is formed, the laminate film meet following (1-i)-(1-v) Important document:
(1-i) complete 80% or more light transmittance；
3.0% or less (1-ii) mist degree；
3 or less (1-iii) yellow index；
100 degree of water contact angle or more of (1-iv) touch surface；And
100 degree of water contact angle or more after the round-trip wiping of 20,000 times of (1-v) touch surface.
[9] manufacturing method of hard conating laminate film described in above-mentioned [8] comprising following process: will contain
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts；And
(D) the particle 5-100 mass parts of average grain diameter 1-300nm
The hard conating formation of active energy line curing resin composition with coating to be coated on poly- (methyl) acryloyl sub- At least single side of amine system resin film, the process for forming hard conating.
[10] manufacturing method of hard conating laminate film described in above-mentioned [8] comprising following process: will contain
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts；
(D) the particle 5-100 mass parts of average grain diameter 1-300nm；And
(E) hydrophobing agent 0.01-7 mass parts
The hard conating formation of active energy line curing resin composition with coating to be coated on poly- (methyl) acryloyl sub- At least single side of amine system resin film, the process for forming hard conating.
[11] method described in above-mentioned [10], wherein above-mentioned (E) hydrophobing agent includes the fluorine containing (methyl) acryloyl group Polyether system hydrophobing agent.
[12] the hard conating laminate film that is manufactured using method described in any one of above-mentioned [9]-[11].
[13] hard conating laminate film described in any one of above-mentioned [4]-[8] and [12] is as image display device component Purposes.
[14] image display device component contains hard coat layers described in any one of above-mentioned [4]-[8] and [12] Close film.
Second aspect of the present invention for reaching above-mentioned second purpose is as described below.
[15] transparent resin lamilate, in order with the layer and transparent resin sheet of hard conating since most surface layer side Layer,
Above-mentioned hard conating is by containing
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts；And
(D) the particle 5-100 mass parts of average grain diameter 1-300nm
Coating formed.
[16] transparent resin lamilate described in above-mentioned [15], wherein above-mentioned hard conating is hydrophobic by further containing (E) The coating of agent 0.1-7 mass parts is formed.
[17] transparent resin lamilate described in above-mentioned [15] or [16], wherein above-mentioned transparent resin sheet is poly- (methyl) Acrylimide series resin sheet.
[18] transparent resin lamilate described in above-mentioned [17], wherein above-mentioned poly- (methyl) acrylimide series resin sheet For directly laminated first poly- (methyl) acrylimide resin in order；Aromatic polycarbonate resin；And second The laminated sheet of poly- (methyl) acrylimide resin.
[19] transparent resin lamilate, it is characterised in that its since most surface layer side in order with hard conating layer and The layer of poly- (methyl) acrylimide series resin sheet, the lamilate meet following characteristics (2-i)-(2-iii):
(2-i) complete 80% or more light transmittance；
5% or less (2-ii) mist degree；And
3 or less (2-iii) yellow index.
[20] purposes of the transparent resin lamilate as vehicle component described in any one of above-mentioned [15]-[19].
[21] purposes of the transparent resin lamilate as building member described in any one of above-mentioned [15]-[19].
[22] vehicle component contains transparent resin lamilate described in any one of above-mentioned [15]-[19].
[23] building member contains transparent resin lamilate described in any one of above-mentioned [15]-[19].
Invention effect
Tool is formed by by the coating of the active energy line curing resin composition containing the above-mentioned first aspect of the present invention There are the transparency, tone, marresistance, surface hardness, flexing resistance and the appearance of the hard conating laminate film of hard conating excellent. Therefore, which can be used as the component of the image display devices such as liquid crystal display, plasma scope, electroluminescent display (including the image display device with touch panel function and not the image display device of touch panel function), especially The display pannel of touch panel properly uses.
In addition, the specific gravity of the transparent resin lamilate of the above-mentioned second aspect of the present invention is small, the transparency, rigidity, scratch resistant Property, weatherability, impact resistance and excellent in workability.Therefore, which can be used as the window or windshield, building of vehicle Window or the furniture such as surface element, the kitchen cabinet of families' electrical article such as door, the protection board of electronic signs, refrigerator door and show window etc. Component properly uses.
Detailed description of the invention
Fig. 1 is the concept map of the device used in the film of transparent resin film (p-1) in embodiment.
Fig. 2 is the concept map of the device used in the film of transparent resin sheet in embodiment.
Specific embodiment
The active energy line curing resin composition of [I] first aspect present invention and the resin combination is used Hard conating laminate film
1. active energy line curing resin composition:
The active energy line curing resin composition of the above-mentioned first aspect of the present invention is illustrated.
(A) multifunctional (methyl) acrylate:
Active energy line curing resin composition of the invention contains (A) multifunctional (methyl) acrylate.
Mentioned component A is that have 2 or more (methyl) acryloyl group (methyl) acrylate in 1 molecule.The compound Due to (methyl) acryloyl group in 1 molecule with 2 or more, plays and utilize ultraviolet light or electron beam isoreactivity energy Line carries out polymerizable/curable, forms the function of hard conating.
As above-mentioned multifunctional (methyl) acrylate, such as diethylene glycol (deg) two (methyl) acrylate, new penta 2 can be enumerated Alcohol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, 2,2 '- Bis- (4- (methyl) acryloxy polyethyleneoxy phenyl) propane and 2,2 '-bis- (4- (methyl) acryloxy polypropylene oxygen Base phenyl) propane etc. contains 2 functional response's property monomers of (methyl) acryloyl group；Trimethylolpropane tris (methyl) acrylate, Trimethylolethane trimethacrylate (methyl) acrylate etc. contains 3 functional response's property monomers of (methyl) acryloyl group；Pentaerythrite four (methyl) acrylate etc. contains 4 functional response's property monomers of (methyl) acryloyl group；Dipentaerythritol hexaacrylate etc. contains 6 functional response's property monomers of (methyl) acryloyl group；And it is (low using a kind or more of these monomers as the polymer for being constituted monomer Polymers or prepolymer).As mentioned component A, one kind or two or more mixture therein can be used.
In addition, (methyl) acrylate refers to acrylate and methacrylate in this specification.
(B) with the compound of alkoxysilyl and (methyl) acryloyl group:
Active energy line curing resin composition of the invention contains (B) with alkoxysilyl and (methyl) The compound of acryloyl group.
Wherein, (methyl) acryloyl group refers to acryloyl group or methylacryloyl.In addition, mentioned component B is with alkane The aspect of oxygroup silicyl is distinguished with mentioned component A.The compound of mentioned component A does not have alkoxysilyl.This theory In bright book, the compound of (methyl) acryloyl group with alkoxysilyl and 2 or more in 1 molecule is ingredient B.
Mentioned component B by intramolecular there is (methyl) acryloyl group can be chemically bonded with mentioned component A or strong Ground interacted, there is alkoxysilyl can be chemically bonded with mentioned component D or consumingly by intramolecular Interaction.Ingredient B has the scratch resistance for greatly improving hard conating by this chemical bonding or strong interaction The effect of property.In addition, ingredient B is by having (methyl) acryloyl group or with alkoxysilyl in the molecule, with Mentioned component E is chemically bonded or consumingly interacts.Ingredient B by it is this chemical bonding or strong interaction, Also acting as prevents the troublesome effects such as ingredient E extravasation.
As mentioned component B, such as can enumerate with general formula " (- SiO2RR’-)n·(-SiO2RR”-)m" shown in chemistry The compound of structure.Wherein, n is natural number (positive integer), and m is 0 or natural number.It is preferred that n be 2-10 natural number, m be 0 or The natural number of 1-10.R is methoxyl group (CH3O-), ethyoxyl (C2H5The alkoxies such as O-).R ' is acryloyl group (CH2= ) or methylacryloyl (CH CHCO-2=C (CH3)CO-).R " is methyl (CH3), ethyl (CH2CH3) etc. alkyl.
As mentioned component B, such as can enumerate with general formula (- SiO2(OCH3) (OCHC=CH2)-)n、(-SiO2 (OCH3)(OC(CH3) C=CH2)-)n、 (-SiO2(OCH3) (OCHC=CH2)-)n·(-SiO2(OCH3)(CH3)-)m、 (- SiO2(OCH3)(OC(CH3) C=CH2)-)n·(-SiO2(OCH3)(CH3)-)m、 (-SiO2(OC2H5) (OCHC=CH2)-)n、(- SiO2(OC2H5)(OC(CH3) C=CH2)-)n、 (-SiO2(OC2H5) (OCHC=CH2)-)n·(-SiO2(OCH3)(CH3)-)mAnd (-SiO2(OC2H5)(OC(CH3) C=CH2)-)n·(-SiO2(OCH3)(CH3)-)mThe compound of shown chemical structure.Wherein, N is natural number (positive integer), and m is 0 or natural number.It is preferred that n is the natural number of 2-10, m is the natural number of 0 or 1-10.
As mentioned component B, one kind or two or more mixture therein can be used.
The use level of mentioned component B is 0.2 relative to 100 mass parts of mentioned component A from the viewpoint of marresistance More than mass parts, more than preferably 0.5 mass parts, more than more preferably 1 mass parts.And from being easy to show hydrophobic viewpoint It sets out, makes from the perspective of ingredient C will not become excess when the match ratio preferred scope of ingredient B and mentioned component C, ingredient B Use level relative to 100 mass parts of mentioned component A be 4 below the mass that preferably 3 below the mass, more preferably 2 Below the mass.
In addition, from the viewpoint of with mentioned component D be chemically bonded or consumingly interact, mentioned component B with it is upper The match ratio of ingredient D is stated usually relative to 100 mass parts of ingredient D, ingredient B is 0.2-80 mass parts, preferably 0.5-15 matter Measure part, more preferably 2-7 mass parts.
(C) organic titanium:
Active energy line curing resin composition of the invention contains (C) organic titanium.
Mentioned component C is the ingredient for assisting the function of mentioned component B.From the sight for the marresistance for greatly improving hard conating Point sets out, and ingredient B and ingredient C show special beneficial affinity.Change in addition, ingredient C is also functioned to itself with mentioned component D etc. It learns bonding or consumingly interacts, improve the effect of the marresistance of hard conating.
As above-mentioned organic titanium, such as tetraisopropoxy titanium, four titanium n-butoxides, four (2- ethyl hexyl oxies) can be enumerated Bis- (levulinic ketone group) titaniums of titanium, isopropoxy octamethylene glycolic titanium, diisopropoxy, bis- (the acetyl second of two oxygroup titanium of propane Acetoacetic ester), tri-n-butoxytitanium monostearate, diisopropoxy titanium distearate, titanium stearate, diisopropoxy titanium Diisopstearate, (2- n-butoxycarbonyl benzoyloxy) three titanium butoxides, two n-butoxies-bis- (triethanolamine) Titanium；And the polymer etc. that their a kind or more is constituted.As mentioned component C, can be used therein one kind or two or more Obtain mixture.
Wherein, from the viewpoint of marresistance and tone, the preferably tetraisopropoxy titanium of alkoxytitanium, four positive fourth oxygen Base titanium, four (2- ethyl hexyl oxy) titaniums and isopropoxy octamethylene glycolic titanium.
The use level of mentioned component C is 0.05 relative to 100 mass parts of mentioned component A from the viewpoint of marresistance More than mass parts, more than preferably 0.1 mass parts, more than more preferably 0.2 mass parts.On the other hand, go out from the viewpoint of tone Hair, the use level of ingredient C are that 3 below the mass, preferably 2 below the mass, more relative to 100 mass parts of mentioned component A Preferably 1.5 below the mass.
In addition, mentioned component B matches with mentioned component C's from the viewpoint of the effect for effectively assisting mentioned component B For composition and division in a proportion usually relative to 100 mass parts of ingredient B, ingredient C is 1.25-1500 mass parts, preferably 5-150 mass parts, more excellent It is selected as 20-80 mass parts.
(D) particle of average grain diameter 1-300nm:
Active energy line curing resin composition of the invention contains the particle of (D) average grain diameter 1-300nm.
Mentioned component D plays the role of improving the surface hardness of hard conating.On the other hand, become the phase with mentioned component A The reason of interaction is weak, becomes inadequate marresistance.Thus, using in the present invention can be with the two of ingredient A and ingredient D The mentioned component C of the effect of person's chemical bonding or the mentioned component B and auxiliary element B that consumingly interact, solves this Problem.
Thus, ingredient D is the substance that can be chemically bonded with mentioned component B or consumingly interact, more preferably It is the substance that can be interacted with mentioned component B and ingredient C chemical bonding or consumingly.
As mentioned component D, can be used inorganic particles, organic fine particles it is any.As inorganic particles, such as can Enumerate silica；Aluminium oxide, zirconium dioxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, The metal oxide microparticles such as antimony oxide, cerium oxide；The metal fluorides particle such as magnesium fluoride, sodium fluoride；Metal sulfide particle； Metal nitride particle；Metal particle etc..As organic fine particles, for example, can enumerate phenylethylene resin series, acrylic resin, The resin beads such as polycarbonate-based resin, the solidified resin of vinylite, amino based compound and formaldehyde.These substances can be with It is used alone a kind or two or more is applied in combination.
It is considered can be at least chemically bonded with ingredient B as exemplary these substances group of ingredient D or consumingly phase The substance of interaction.
In addition, improving the surface hardness of gained hard conating to improve dispersibility of the particle in coating, also can be used Utilize the silane series coupling agents such as vinyl silanes, amino silane；Titanate esters system coupling agent；Aluminate-series coupling agent；With (first Base) the ethylene linkages unsaturated bond such as acryloyl group, vinyl, allyl or epoxy group isoreactivity functional group organic compound； Surface treating agents such as fatty acid, fatty acid metal salts etc. have carried out processor to the surface of the particle.
In these particles, in order to obtain the higher hard conating of surface hardness, the preferably particle of silica or aluminium oxide, The particle of more preferable silica.As the commercially available product of silicon dioxide microparticle, Nissan Chemical Ind Ltd can be enumerated Snowtex (trade name), Quattron (trade name) of Fukawa Chemical Industries Co., Ltd. etc..
The average grain diameter of mentioned component D obtains the table of hard conating from the transparent viewpoint for keeping hard conating and certainly It is 300nm or less from the perspective of surface hardness improved effect.The average grain diameter of ingredient D is preferably 200nm hereinafter, more preferably 120nm or less.On the other hand, the lower limit for limiting average grain diameter has no special reason, but the particle that usually can be obtained most it is thin not Cross 1nm or so.
In addition, the average grain diameter of particle is in laser diffraction/scattering formula using Nikkiso Company Limited in this specification In the grading curve of grain size analysis meter " MT3200II (trade name) " measurement, accumulates and reach since the small side of particle The partial size of 50 mass %.
The use level of mentioned component D is 5 matter relative to 100 mass parts of mentioned component A from the viewpoint of surface hardness Part or more is measured, more than preferably 20 mass parts.On the other hand, from the viewpoint of marresistance and the transparency, ingredient D's matches Resultant is 100 below the mass that preferably 70 below the mass, more preferably 50 matter relative to 100 mass parts of mentioned component A Measure part or less.
(E) hydrophobing agent:
In active energy line curing resin composition of the invention from improve finger sliding property, dirt-proof adhesion and It is preferably further (multifunctional relative to (A) containing (E) hydrophobing agent 0.01-7 mass parts from the perspective of the property wiped away of dirt The amount of 100 mass parts of (methyl) acrylate).
As above-mentioned hydrophobing agent, such as the waxes systems such as paraffin, polyethylene wax, acrylic acid ethylene co-polymer wax can be enumerated and dredged Aqua；The silicon systems hydrophobing agent such as silicone oil, silicone resin, dimethyl silicone polymer, alkylalkoxy silane；Perfluoroalkyl polyether system hydrophobing agent, fluorine Poly- alkyl system hydrophobing agent etc. is containing fluorine system water-repelling agent etc..As mentioned component E, therein one kind or two or more mix can be used Close object.
In these hydrophobing agents, the preferred perfluoroalkyl polyether system hydrophobing agent from the viewpoint of hydrophobic performance.From mentioned component A or on Ingredient B and ingredient E is stated to carry out from the perspective of being chemically bonded or consumingly interact, preventing the troubles such as ingredient E exudation, As ingredient E, the hydrophobing agent that the compound of (methyl) acryloyl group and perfluoroalkyl polyether base is more preferably included containing molecule is (following Slightly it is denoted as the perfluoroalkyl polyether system hydrophobing agent containing (methyl) acryloyl group).As ingredient E, from suitably modifying ingredients A or ingredient B Chemical bonding or interaction with ingredient E show good hydrophobic viewpoint while height keeps the transparency and go out Hair can also use the mixed of perfluoroalkyl polyether system hydrophobing agent containing acryloyl group and the perfluoroalkyl polyether system hydrophobing agent containing methylacryloyl And object.
Use level when using mentioned component E from the viewpoint of preventing the troubles such as ingredient E exudation, relative to it is above-mentioned at Point 100 mass parts of A are usually that 7 below the mass, preferably 4 below the mass, and more preferably 2 below the mass.Ingredient E's Use level lower limit is not particularly limited, but from the viewpoint of obtaining required effect, usually due to being any ingredient More than 0.01 mass parts, more than preferably 0.05 mass parts, more than more preferably 0.1 mass parts.
In addition, in active energy line curing resin composition of the invention, from making active energy ray bring curability From the perspective of becoming good, preferably comprise compound in 1 molecule with 2 or more isocyanate group (- N=C=O) and/ Or Photoepolymerizationinitiater initiater.
As the compound in above-mentioned 1 molecule with 2 or more isocyanate group, such as di-2-ethylhexylphosphine oxide -4- ring can be enumerated Hexyl isocyanates；The trihydroxy methyl of the trimethylolpropane adduct of toluene di-isocyanate(TDI), hexamethylene diisocyanate Propane adduct, the trimethylolpropane adduct of isophorone diisocyanate, toluene di-isocyanate(TDI) chlorinated isocyanurates Body, the chlorinated isocyanurates body of hexamethylene diisocyanate, the chlorinated isocyanurates body of isophorone diisocyanate, six methylenes The polyisocyanate such as the biuret body of group diisocyanate；And the amino of block type isocyanates of above-mentioned polyisocyanate etc. Formic acid esters crosslinking agent etc..As the compound in above-mentioned 1 molecule with 2 or more isocyanate group, therein 1 can be used Kind or mixture of more than two kinds.In addition, dibutyl tin dilaurate, diethyl can also be added as needed in crosslinking The catalyst such as caproic acid dibutyl tin.
As above-mentioned Photoepolymerizationinitiater initiater, such as benzophenone, methyl-o- benzoylbenzoate, 4- first can be enumerated Base benzophenone, 4,4 '-bis- (diethylamino) benzophenone, o- benzoyl methyl benzoate, 4- phenyl benzophenone, 4- benzoyl -4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 2,4,6- The benzophenone based compounds such as tri-methyl benzophenone；Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin are different The benzoins based compound such as propyl ether, benzylmethylketal；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 1- hydroxyl The acetophenones based compound such as cyclohexyl-phenyl ketone；The anthraquinones based compounds such as tectoquinone, 2- ethyl hydrazine, 2- acyl group anthraquinone；Thiophene The thioxanthones based compounds such as ton ketone, 2,4- diethyl thioxanthone, 2,4- diisopropylthioxanthone；Acetophenone dimethyl ketal etc. Alkyl acyl benzene compounds；Triazine based compound；United imidazole；Acylphosphine oxide compound；Titanium saves based compound； Oxime ester based compound；Oxime phenylacetate based compound；Hydroxy-ketone based compound；And Aminobenzoate based compound etc..Make For above-mentioned Photoepolymerizationinitiater initiater, one kind or two or more mixture therein can be used.
In addition, active energy line curing resin composition of the invention can also be as needed containing one kind or two or more Antistatic agent, surfactant, levelling agent, rheological characteristic imparting agent, antistain agent, printing modifying agent, antioxidant, resistance to The additives such as time property stabilizer, light resistance stabilizer, ultraviolet absorbing agent, heat stabilizer, colorant and filler.
In addition, active energy line curing resin composition of the invention may be used also to be diluted to the concentration for being easy to cover with paint, lacquer, colour wash, etc. Contain solvent as needed.As long as solvent is reacted with mentioned component A-D and other any ingredients, it will not be catalyzed and (promote Into) solvent of the autoreactions (including deterioration reaction) of these ingredients, then it is not particularly limited.As solvent, such as 1- first can be enumerated Oxygroup -2- propyl alcohol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diacetone alcohol and acetone etc..
Above-mentioned active energy line curing resin composition is obtained by being mixed, being stirred to these ingredients.
2. hard conating laminate film:
The hard conating laminate film of the above-mentioned first aspect of the present invention is illustrated.
Hard conating laminate film of the invention is preferably formed by at least single side in transparent resin film by living containing the present invention Property energy line curing resin composition the hard conating that constitutes of coating obtain.
Above-mentioned hard conating is formed in at least single side of above-mentioned transparent resin film, the preferred shape from the viewpoint of resistance to bend(ing) At in two faces of above-mentioned transparent resin film.
It is preferred that hard conating laminate film has the first hard conating in order since most surface layer side；Transparent resin film layer；And the Two hard conatings, wherein the first hard conating is formed by the coating containing active energy line curing resin composition of the present invention.
Wherein " surface layer side " refers to that distance is formed by article as the hard conating zoarium of multi-ply construction and makes at the scene of being supplied to The outside (touch surface when touch panel display panel) of used time is closer.
In turn, above-mentioned hard conating possessed by above-mentioned hard conating laminate film is not limited to 1 layer, is also possible to 2 layers or more.Separately Outside, transparent resin film layer is not limited to 1 layer, can also be 2 layers or more.In turn, hard conating laminate film can also have hard as needed Random layer other than coating and transparent resin film.As random layer, such as cementation coating, adhesive phase, electrically conducting transparent can be enumerated Layer, high refractive index layer, low-index layer and anti-reflective function layer etc..
Hard painting is formed with coating using the hard conating formation containing active energy line curing resin composition of the invention The method of layer is not particularly limited, and well known net formula coating method can be used.Roller coating, intaglio plate coating, anti-can specifically be enumerated The methods of formula coating, roller brush, spraying, airblade coating and die head coating.
The thickness of above-mentioned hard conating is not particularly limited, from the surface hardness of hard conating laminate film, rigidity, heat resistance and It can be usually 1 μm or more from the perspective of dimensional stability, preferably 5 μm or more, more preferably 10 μm or more, further Preferably 20 μm or more.In addition, the thickness of above-mentioned hard conating is handled from the machining adaptability or net formula of hard conating laminate film It can be preferably 100 μm hereinafter, more preferably 50 μm or less from the perspective of property.
Above-mentioned transparent resin film is the layer as the transparent film base material for being used to form above-mentioned hard conating.As above-mentioned transparent Resin film is not particularly limited other than with high transparency and no coloring, arbitrary transparent resin film can be used.
The cellulose esters such as triacetyl cellulose system resin can be for example enumerated as transparent resin film；Poly terephthalic acid second The polyester based resins such as diol ester；The ring-type hydrocarbon system resin such as vinyl norbornene copolymer；Polymethyl methacrylate, poly- methyl The acrylic resins such as ethyl acrylate；Poly- (methyl) acrylimide system resin；Aromatic polycarbonate system resin；Polypropylene, The polyolefin-based resins such as 4- methyl pentene -1；Polyamide resin；Polyacrylate system resin；Polymer-type carbamic acid Ester acrylic ester resin；And the films such as polyimides system resins.Transparent resin film includes no stretched PTFE film, uniaxial extension film and double Axis stretched PTFE film.In addition, also including their one kind or two or more laminate film.
Above-mentioned preferably poly- (methyl) the acrylimide resin film of transparent resin film.By using poly- (methyl) propylene Imide series resin film becomes surface hardness, marresistance, the transparency, surface smoothness, appearance, rigidity, heat resistance and ruler The hard conating laminate film of very little excellent in stability, the display pannel or transparent conductive substrate that can be used as touch panel are suitably It uses.
Above-mentioned poly- (methyl) acrylimide system resin is the high transparency, high surface hardness, height in acrylic resin It is introduced directly into the heat resistance of polyimides system resins or the feature of excellent in dimensional stability in the feature of rigidity, improves coloring At the thermoplastic resin of faint yellow to russet disadvantage.Poly- (methyl) acrylimide system resin is for example disclosed in Japanese spy In table 2011-519999 bulletin.In the present specification, poly- (methyl) acrylimide refers to polyacrylimide or poly- first Base acrylimide.
As above-mentioned poly- (methyl) acrylimide system resin, the optics such as touch panel are used for from by hard conating laminate film Purpose in article is set out, and is not particularly limited other than with high transparency and no coloring, arbitrary public affairs can be used Know poly- (methyl) acrylimide system resin.
As the preferred person of above-mentioned poly- (methyl) acrylimide system resin, yellow index can be enumerated (according to JIS K7105:1981 is measured using the colorimeter " SolidSpec-3700 (trade name) " of Shimadzu Scisakusho Ltd) be 3 or less persons.The yellow index of poly- (methyl) acrylimide system resin is more preferably 2 hereinafter, further preferably 1 or less.
In addition, from the viewpoint of squeezing out the stability of load or fused film, it is sub- as preferred poly- (methyl) acryloyl Amine system resin, can enumerate melt flow rate (MFR) (according to ISO1133, measuring under conditions of 260 DEG C, 98.07N) is 0.1- 20g/10 minute person.The melt flow rate (MFR) of poly- (methyl) acrylimide system resin is more preferably 0.5-10g/10 minutes.
In turn, the glass transition temperature of poly- (methyl) acrylimide system resin is preferred from the viewpoint of heat resistance It is 150 DEG C or more.Glass transition temperature is more preferably 170 DEG C or more.
In addition, above-mentioned poly- (methyl) as long as do not violate the object of the invention in acrylimide system resin, it can also be according to need It will be further containing the thermoplastic resin other than poly- (methyl) acrylimide system resin；Pigment, organic is filled out inorganic filler Fill agent, resin filler；Lubricant, antioxidant, weatherability stabilizer, heat stabilizer, release agent, antistatic agent and surface Additives such as activating agent etc..The use level of these any ingredients usually makes poly- (methyl) acrylimide system resin 100 It is 0.01-10 mass parts or so when mass parts.
As the commercially available example of above-mentioned poly- (methyl) acrylimide system resin, " the PLEXIMID of Evonik company can be enumerated TT70 (trade name) " etc..
Above-mentioned poly- (methyl) acrylimide resin film is preferably directly laminated in order the first poly- (methyl) propylene Imide series resin layer (α 1)；Aromatic polycarbonate resin (β)；Second poly- (methyl) acrylimide resin (α 2) transparent multilayer film.Wherein, touch surface person is formed as in the 1 layer of side above-mentioned α in this specification, illustrates hard conating laminate film.
Poly- (methyl) acrylimide system resin in general heat resistance or surface hardness is excellent, but machinability is easy In becoming insufficient.Corresponding thereto, although aromatic polycarbonate system resin machinability is excellent, heat resistance or surface hardness It is easy to become insufficient.Therefore, the transparent multilayer film constituted by using above-mentioned layer can be readily available and make up the weak of the two The excellent hard conating laminate film of point, heat resistance, surface hardness and machinability.
The thickness of 1 layer of above-mentioned α is not particularly limited, from the heat resistance or surface hardness of hard conating laminate film of the invention From the perspective of, usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more.
The thickness of 2 layers of above-mentioned α is not particularly limited, and is gone out from the viewpoint of the resistance to bend(ing) of hard conating laminate film of the invention Hair, preferably with 1 layer of identical thickness of above-mentioned α.
In addition, " identical thickness " should not be construed as identical thickness on physicochemical stricti jurise here. It should be construed to, be identical thickness in process/qualitative control amplitude range that industry usually carries out.The reason is that As long as being identical thickness in the process/qualitative control amplitude range industrially usually carried out, then it can keep well more The resistance to bend(ing) of tunic.When for using T die head coetrusion without multilayer film is extended, usually with -5 to+5 μm or so of amplitude Process/qualitative control is carried out, therefore 65 μm and 75 μm of thickness of thickness should be construed to identical.Here " identical thickness " may be used also It in other words is " substantially the same thickness ".
Above-mentioned β layers of thickness is not particularly limited, from the resistance to machinability viewpoint of hard conating laminate film of the invention, It can be usually 20 μm or more, preferably 80 μm or more, more preferably 120 μm or more.
It is as described above for poly- (methyl) acrylimide system resin used in 1 layer of above-mentioned α and 2 layers of above-mentioned α.
In addition, poly- (first used in poly- (methyl) acrylimide system's resin used in 1 layer of above-mentioned α and 2 layers of above-mentioned α Base) different resins characteristic person can be used in acrylimide system resin, such as melt flow rate (MFR) or glass transition temperature are not Same poly- (methyl) acrylimide system resin.But the viewpoint of the resistance to bend(ing) from hard conating laminate film of the invention goes out Hair more preferably uses same resin characteristic person.For example, using the same batch of same levels for 1 layer of α and 2 layers of α Poly- (methyl) acrylimide system resin be one of preferred embodiment.
As aromatic polycarbonate system resin used in β layers above-mentioned, can be used for example bisphenol-A, dimethyl bisphenol A, Bis- (4- hydroxy phenyl) -3,3,5- trimethyl-cyclohexanes of 1,1- etc. pass through the interfacial polymerization of aromatic dihydroxy compound and phosgene The polymer that method obtains；Bis- (4- hydroxy phenyl) -3,3,5- trimethyl-cyclohexanes of bisphenol-A, dimethyl bisphenol A, 1,1- etc. pass through The poly- carbon of aromatics such as the polymer that the ester exchange reaction of the carbonic diesters such as aromatic dihydroxy compound and diphenyl carbonate obtains The one kind or two or more mixture of acid esters system resin.
As the preferred any ingredient that can contain in above-mentioned aromatic polycarbonate system resin, core shell rubber can be enumerated Glue.When making 100 mass parts of total amount of aromatic polycarbonate system resin and core shell rubber, by with 0-30 mass parts (aromatics Polycarbonate-based resin 100-70 mass parts), preferably 0-10 mass parts (aromatic polycarbonate system resin 100-90 mass parts) Amount use core shell rubber, can be further improved resistance to machinability or impact resistance.
As above-mentioned core shell rubber, such as methacrylate styrene/butadiene rubbers graft copolymerization can be enumerated Object, acrylonitrile styrene/butadiene rubber graft copolymer, acrylonitrile styrene/ethylene propylene rubber graft copolymerization Object, acrylonitrile styrene/acrylate graft copolymers, methacrylate/acrylate rubber graft copolymer, first The core shells rubber such as base acrylate acrylonitrile/acrylate rubber graft copolymer.Can be used these a kind or 2 kinds with On core shell rubber mixture.
As long as, can also further basis in addition, do not violate the object of the invention in above-mentioned aromatic polycarbonate system resin It needs containing the thermoplastic resin other than aromatic polycarbonate system resin or core shell rubber；Pigment, organic is filled out inorganic filler Fill agent, resin filler；Lubricant, antioxidant, weatherability stabilizer, heat stabilizer, release agent, antistatic agent and surface Additives such as activating agent etc..The use level of these any ingredients usually makes aromatic polycarbonate system resin and core shell rubber It is 0.01-10 mass parts or so when total amount is 100 mass parts.
Manufacturing method for obtaining above-mentioned poly- (methyl) acrylimide resin film is not particularly limited, such as can To enumerate the method including following process: (A) continuously squeezes out poly- using the device for having extruder and T die head, from T die head The process of the fused film of (methyl) acrylimide system resin；(B) the first specular surface body for being rotated or being recycled with revolved Turn or the second specular surface body of circulation between supply put into fused film and the progress of above-mentioned poly- (methyl) acrylimide system resin The process of extruding.
Equally, in order directly laminated 1 layer of above-mentioned α, β layers, the manufacturing method of 2 layers of α of transparent multilayer film have no special limit Fixed, for example, including the method for following process: (A ') uses the co-extrusion device for having extruder and T die head, from T Die head directly laminated in order will have the first poly- (methyl) acrylimide resin (α 1)；Aromatic polycarbonate system resin Layer (β)；What the fused film of the transparent multilayer film of the second poly- (methyl) acrylimide resin (α 2) was continuously coextruded Process；(B ') in the first specular surface body for being rotated or being recycled and rotated or the second specular surface body for recycling between supply and throw The process for entering the fused film of above-mentioned transparent multilayer film and being squeezed.
As above-mentioned T die head used in above-mentioned operation (A) or above-mentioned operation (A '), any known mould can be used Head.Such as manifold die, fish tail coventry type die head coventry and hanger-style die can be enumerated etc..
As above-mentioned co-extrusion device, arbitrary known person can be used.For example, feeding block mode, more discriminations can be enumerated The co-extrusion devices such as pipe mode and lamination mode.
As above-mentioned extruder used in above-mentioned operation (A) or above-mentioned operation (A '), can be used arbitrary known Person.For example, single axle extruding machine, equidirectional rotation biaxial extruder and different direction rotate biaxial extruder etc..
In addition, the deterioration in order to inhibit poly- (methyl) acrylimide system's resin or aromatic polycarbonate system resin, to crowded Carrying out nitrogen purging in machine out is also one of preferred method.
In turn, poly- (methyl) acrylimide system's resin is due to being bibulous resin, before being supplied to film It is preferred that it is dried.In addition, by poly- (methyl) the acrylimide system's resin dried with drying machine from drying machine It is fed directly to extruder and carries out investment be also one of preferred method.The set temperature of drying machine is preferably 100-150 DEG C.Separately Outside, (the usually metering region of propeller front end) setting vacuum ventilation mouth is also one of preferred method in extruder.
The temperature of above-mentioned T die head used in above-mentioned operation (A) or above-mentioned operation (A '), in order to steadily carry out gathering The work of the fused film of (methyl) acrylimide system resin or the fused film of above-mentioned transparent multilayer film continuously extrusion or co-extrusion Sequence is preferably at least set in 260 DEG C or more.More preferably 270 DEG C or more.In addition, in order to inhibit poly- (methyl) acrylimide It is the deterioration of resin or aromatic polycarbonate system resin, the temperature of T die head is preferably set to 350 DEG C or less.
In addition, the ratio between thickness (T) of die gap (R) and poly- (methyl) the acrylimide film of gained (R/T) from delay not From the perspective of becoming larger, preferably 10 hereinafter, more preferably 5 or less.In addition, will not become than (R/T) from load is squeezed out From the perspective of big, preferably 1 or more, more preferably 1.5 or more.
As above-mentioned first specular surface body used in above-mentioned operation (B) or above-mentioned operation (B '), such as mirror roller can be enumerated Or mirror surface band etc..As above-mentioned second specular surface body, such as mirror roller or mirror surface band etc. can be enumerated.
Above-mentioned mirror roller is roll of its surface Jing Guo mirror finish.The material of mirror roller has made of metal, ceramic system and silicon Rubber system etc..In addition, for the surface of mirror roller, for the purpose of being protected from corrosion or scratch, it is possible to implement chromium plating or Iron-phosphorus alloy plating, the hard carbon processing carried out using PVD method or CVD method etc..
Above-mentioned mirror surface band is its surface by mirror finish, usually metal endless belt.Mirror surface band is for example hung over It is recycled between a pair of band roll.In addition, for the surface of mirror surface band, to be protected from corrosion or scratch as mesh , chromium plating or iron-phosphorus alloy plating, the stearic carbon processing carried out using PVD method or CVD method etc. can also be implemented.
Above-mentioned mirror finish is simultaneously not limited, and can use arbitrary method progress.For example, can enumerate by using fine Abrasive grains ground, the arithmetic average roughness (Ra) for making above-mentioned specular surface body surface is preferably 100nm hereinafter, more excellent 50nm is selected as hereinafter, 10 mean roughness (Rz) are preferably 500nm hereinafter, more preferably 250nm the following method.
Although the intention not constrained theoretically, the transparency is obtained by above-mentioned film-forming method, surface is put down Poly- (methyl) the acrylimide resin film or transparent multilayer film of slip and excellent appearance can consider the reason is as follows that: pass through Using the first specular surface body and the second specular surface body to the fused film of poly- (methyl) acrylimide resin film or transparent multilayer film into Row squeezes, and the smooth surface state of the height of the first specular surface body and the second specular surface body is transferred on film, die head striped is had modified Etc. defective works.
In order to carry out the transfer of above-mentioned surface state well, the surface temperature of the first specular surface body is preferably 100 DEG C or more. Its surface temperature is more preferably 120 DEG C or more, further preferably 130 DEG C or more.And it is presented in film in order to prevent adjoint with The bad order (removing trace) of the removing of one specular surface body, the surface temperature of the first specular surface body is preferably 200 DEG C hereinafter, more preferably It is 160 DEG C or less.
In order to carry out the transfer of above-mentioned surface state well, the surface temperature of the second specular surface body is preferably 20 DEG C or more.Its Surface temperature is more preferably 60 DEG C or more, further preferably 100 DEG C or more.And it is presented in film in order to prevent adjoint with second The bad order (removing trace) of the removing of specular surface body, the surface temperature of the second specular surface body is preferably 200 DEG C hereinafter, more preferably 160 DEG C or less.
Additionally, it is preferred that keeping the surface temperature of the first specular surface body also higher than the surface temperature of the second specular surface body.This is because will Film is maintained in the first specular surface body, is sent in next transfer roller.
In addition, becoming above-mentioned poly- (methyl) for being used to form the transparent film base material of hard conating when forming above-mentioned hard conating The hard conating forming face or two sides of acrylimide resin film or transparent multilayer film are strong with the bonding of hard conating in order to improve Degree can also implement Corona discharge Treatment or cementation coating is formed etc. easy binder-treatment in advance.
When implementing above-mentioned Corona discharge Treatment, by making wetting index (being measured according to JIS K6768:1999) be usually 50mN/m or more, preferably 60mN/m or more can obtain good bond strength between layers.Furthermore it is also possible to implementing corona After discharge treatment, cementation coating is formed.
Corona discharge Treatment is to pass through film between the electrode to have insulated and dielectric roller, applies high-frequency high voltage, is produced Raw corona discharge, handles film surface.By the corona discharge, oxygen etc. is ionized, by striking against film surface, Cause the addition of the cutting or oxygen-containing functional group of molecular resin chain in molecular resin chain on the surface of the film, wetting index improves.
The per unit area of above-mentioned Corona discharge Treatment, the treating capacity of unit time (S) are by obtaining above-mentioned wetting index Viewpoint determines, usually 80Wmin/m2More than, preferably 120Wmin/m2More than.In addition, from the sight for the deterioration for preventing film Point sets out, and treating capacity (S) is preferably suppressed to 500Wmin/m2Below.Treating capacity (S) is more preferably 400Wmin/m2Below.
In addition, treating capacity (S) is defined with following formula.
S=P/ (LV)
Wherein, S: treating capacity (Wmin/m2), P: discharge energy (W), L: the length (m) of discharge electrode, V: linear velocity (m/min)。
As the cementation coating agent for being used to form above-mentioned cementation coating, other than with high transparency and no coloring, And it is not limited.As cementation coating agent, such as polyester, acrylic acid, polyurethanes, propenoic methyl carbamate can be used And substance well known to polyester urethane etc..Wherein, preferably hot from the viewpoint of being improved with the adhesion strength of hard conating Plasticity carbamate system cementation coating agent.
In addition, the coating containing silane coupling agent can also be used as above-mentioned cementation coating agent.Silane coupling agent is With hydrolization group (such as alkoxies such as methoxyl group, ethyoxyl；The acyloxy such as acetoxyl group；Halogens such as chloro etc.) and have Machine functional group (such as amino, vinyl, epoxy group, methacryloxy, acryloxy and isocyanate group etc.) is extremely The silane compound of few 2 kinds of differential responses groups.This silane coupling agent plays the adhesion strength of raising and hard conating Effect.Wherein, from the viewpoint of being improved with the adhesion strength of hard conating, preferably with the silane coupling agent of amino.
Coating containing above-mentioned silane coupling agent is contained as principal component (being 50 mass % or more as solid content) The coating of silane coupling agent.It is preferred that the 75 mass % or more of the solid content of above-mentioned coating, the above are silicon by more preferable 90 mass % Alkane coupling agent.
As the silane coupling agent with above-mentioned amino, such as N-2- (amino-ethyl) -3- amino propyl methyl can be enumerated Dimethoxysilane, N-2- (amino-ethyl) -3- TSL 8330, N-2- (amino-ethyl) -3- aminopropyl Triethoxysilane, 3- TSL 8330,3-aminopropyltriethoxysilane, 3- triethoxy-silicane Base-N- (1,3- dimethyl-butylidene) propyl amine, N- phenyl -3- TSL 8330, N- (vinyl benzyl) - 2- amino-ethyl -3- TSL 8330 etc..As the silane coupling agent with amino, can be used therein One kind or two or more mixture.
The method of cementation coating is formed using above-mentioned cementation coating agent and is not limited, and well known method can be used.Specifically Ground can enumerate the methods of roller coating, intaglio plate coating, trans- coating, roller brush, spraying, air knife coating method and die head coating.At this point, can With as needed use arbitrary retarder thinner, such as methanol, ethyl alcohol, 1- methoxy-2-propanol, n-butyl acetate, toluene, Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl acetate and acetone etc..
As long as can also contain one kind or two or more in addition, not violating the purpose of the present invention in above-mentioned cementation coating agent Antioxidant, weatherability stabilizer, light resistance stabilizer, ultraviolet absorbing agent, heat stabilizer, antistatic agent, surface-active Agent, colorant, infrared ray block the additives such as agent, levelling agent, rheological characteristic imparting agent and filler.
The thickness of above-mentioned cementation coating is usually 0.01-5 μm or so, and preferably 0.1-2 μm.
The thickness of above-mentioned transparent resin film is not particularly limited, from the viewpoint of treatability, can be usually 20 μm with On, preferably 50 μm or more.Using hard conating laminate film of the invention as touch panel display pannel carry out in use, From the viewpoint of keeping rigidity, the thickness of transparent resin film can be usually 100 μm or more, and preferably 200 μm or more, more Preferably 300 μm or more.In addition, from the viewpoint of the slimming requirement that can cope with touch panel, transparent resin film Thickness can be usually 1500 μm hereinafter, preferably 1200 μm hereinafter, more preferably 1000 μm or less.When suitable for touch surface When not needing the use of high rigidity other than the display pannel of plate on the way, from the viewpoint of economy, the thickness of transparent resin film It can be usually 250 μm hereinafter, preferably 150 μm or less.
Hard conating laminate film of the invention uses Nippon Denshoku Industries Co., Ltd. according to JIS K7361-1:1997 Haze meter " NDH2000 (trade name) " when being measured, preferably full light transmittance is 80% or more.By for full light Hard conating laminate film can be suitably used for the display pannel etc. of touch panel by the high transparency person of 80% or more transmissivity In.The full light transmittance the high the more preferred, and more preferably 85% or more, more preferably 90% or more.
Hard conating laminate film of the invention uses Nippon Denshoku Industries Co., Ltd. according to JIS K7136:2000 When haze meter " NDH2000 (trade name) " is measured, preferably mist degree is 3.0% or less.By for mist degree 3.0% it is below Hard conating laminate film can be preferably used in display pannel of touch panel etc. by high transparency person.The lower mist degree the more excellent Choosing, more preferably 2.0% hereinafter, more preferably 1.5% or less.
Hard conating laminate film of the invention according to JIS K7105:1981, use the coloration of Shimadzu Seisakusho Ltd.'s corporation When meter " SolidSpec-3700 (trade name) " is measured, preferably yellow index is 3 or less.By for yellow index 3 Hard conating laminate film can be preferably used in display pannel of touch panel etc. by uncolored person below.Yellow chromaticity refers to The number the low the more preferred, and more preferably 2 hereinafter, more preferably 1 or less.
It carries out hard conating laminate film of the invention as the display pannel of touch panel in use, it is preferred that hard conating The touch surface of laminate film is 100 degree or more using the water contact angle that the method for following (4) (embodiment) measures.Here hard painting " touch surface " of layer laminate film refers to that becoming for touch panel display panel is touched with finger or style of writing, carries out input operation The face of the side.By water contact angle be 100 degree or more, in the touch surface of hard conating laminate film as streak finger with thinking Or pen, touch panel can be operated.From the viewpoint of as slide finger or pen with thinking, preferably water contact angle is high, More preferably 105 degree or more.On the other hand, the upper limit of water contact angle has no especially, but from the viewpoint of finger sliding property, Usual 120 degree or so i.e. enough.
Using hard conating laminate film of the invention as the display pannel of touch panel in use, it is preferred that hard conating is laminated The touch surface of film using the method for following (5) (embodiment) measure be wiped repeatedly for 20,000 times after water contact angle be 100 degree with On.Water contact angle after being wiped repeatedly by 20,000 times of touch surface is 100 degree or more, is even wiped repeatedly with handkerchief etc. It can maintain the surface characteristic of finger sliding property etc..Water contact angle after being wiped repeatedly for 20000 times is preferably 105 degree or more.And 20,000 It is secondary be wiped repeatedly after the upper limit of water contact angle have no especially, from the viewpoint of finger sliding property, usual 120 degree or so are Enough.
The transparent resin lamilate of [II] second aspect of the present invention
The transparent resin lamilate of the above-mentioned second aspect of the present invention is illustrated.
" piece " this term also includes film or plate in this specification.
In addition, " resin " this term also includes the resin compound or resinous containing 2 or more resins in this specification The resin combination of ingredient in addition.
Transparent resin lamilate of the invention is since most surface layer side in order with the layer and transparent resin sheet of hard conating Layer.The transparent resin lamilate from as replace the material of glass carry out using purpose, have and high transparency and do not have There is coloring.The meaning of " surface layer side " here is as described above.
Transparent resin lamilate of the invention at least has hard conating in the most surface layer side surface of the layer of transparent resin sheet Layer.In turn, transparent resin lamilate of the invention can also have hard conating on another surface of the layer of transparent resin sheet Layer.
1. the active energy line curing resin composition of hard conating formation
Hard conating on the most surface layer side surface of the layer of transparent resin sheet is by containing active energy ray-curable resin combination The coating of object is formed, scoring resistance or excellent scratch resistance.
The coating containing the active energy line curing resin composition is illustrated below.
(A) multifunctional (methyl) acrylate:
It is used to form active energy ray-curable used in the hard conating of the transparent resin lamilate of above-mentioned second aspect Resin combination contains (A) multifunctional (methyl) acrylate.
As the multifunctional (methyl) acrylate, the nothing as long as there are 2 or more (methyl) acryloyl groups in 1 molecule It is particularly limited to, person identical as the active energy line curing resin composition of above-mentioned first aspect can be used.
(B) with the compound of alkoxysilyl and (methyl) acryloyl group:
It is used to form active energy ray-curable used in the hard conating of the transparent resin lamilate of above-mentioned second aspect Resin combination contains the compound that (B) has alkoxysilyl and (methyl) acryloyl group.
Wherein, (methyl) acryloyl group refers to acryloyl group or methylacryloyl.Wherein, mentioned component B is with alkane Oxygroup silicyl this point is distinguished with mentioned component A.The compound of mentioned component A does not have alkoxysilyl.This theory In bright book, the compound with alkoxysilyl and 2 or more (methyl) acryloyl group in 1 molecule is ingredient B.
As the compound with alkoxysilyl He (methyl) acryloyl group, as long as the scope of this definition is then It is not particularly limited, person identical as the active energy line curing resin composition of above-mentioned first aspect can be used.In addition, tool There is the use level of the compound of alkoxysilyl and (methyl) acryloyl group can also be with the active energy of above-mentioned first aspect Amount line hardening resin composition similarly adjusts.
(C) organic titanium:
It is used to form active energy ray-curable used in the hard conating of the transparent resin lamilate of above-mentioned second aspect Resin combination contains (C) organic titanium.
As the organic titanium, can be used identical as the active energy line curing resin composition of above-mentioned first aspect Person.In addition, the use level of organic titanium can also be in the same manner as the active energy line curing resin composition of above-mentioned first aspect Adjustment.
(D) particle of average grain diameter 1-300nm:
It is used to form active energy ray-curable used in the hard conating of the transparent resin lamilate of above-mentioned second aspect Resin combination contains the particle of (D) average grain diameter 1-300nm.
As the particle, person identical as the active energy line curing resin composition of above-mentioned first aspect can be used. In addition, the use level of particle can also adjust in the same manner as the active energy line curing resin composition of above-mentioned first aspect.
(E) hydrophobing agent:
From the viewpoint of improving the property wiped away of dirt preventing property of attachment and dirt, it is used to form above-mentioned second aspect Active energy line curing resin composition used in the hard conating of transparent resin lamilate preferably also contains (E) hydrophobing agent.
As the hydrophobing agent, can be used identical as the active energy line curing resin composition of above-mentioned first aspect Person.In addition, the use level of hydrophobing agent can also be in the same manner as the active energy line curing resin composition of above-mentioned first aspect Adjustment.
In addition, in above-mentioned active energy line curing resin composition, from becoming active energy ray bring curability From the perspective of good, preferably further containing the compound in 1 molecule with 2 or more isocyanate group (- N=C=O) And/or Photoepolymerizationinitiater initiater.
Cause as the compound and photopolymerization in this 1 molecule with 2 or more isocyanate group (- N=C=O) Person identical as the active energy line curing resin composition of above-mentioned first aspect can be used in agent.
Above-mentioned active energy line curing resin composition can also contain one kind or two or more antistatic as needed Agent, surfactant, levelling agent, rheological characteristic imparting agent, antistain agent, printing modifying agent, antioxidant, weatherability are stablized The additives such as agent, light resistance stabilizer, ultraviolet absorbing agent, heat stabilizer, colorant and filler.
Above-mentioned active energy line curing resin composition, can also be according to need in order to be diluted to the concentration for being easy to cover with paint, lacquer, colour wash, etc. Contain solvent.As long as solvent will not be reacted with mentioned component A-D and other any ingredients, will not be catalyzed (promotion) these The autoreaction (including deterioration reaction) of ingredient, then be not particularly limited.As this solvent, can be used and above-mentioned first aspect The identical solvent of active energy line curing resin composition.
Above-mentioned active energy line curing resin composition is obtained by being mixed, being stirred to these ingredients.
2. the layer of hard conating
Hard conating is formed using the coating of the hard conating formation containing above-mentioned active energy line curing resin composition Method is not particularly limited, and well known rotation coating method can be used.Specifically, roller coating, intaglio plate coating, anti-can be enumerated The methods of formula coating, roller brush, spraying, air knife coating method and die head coating.
The thickness of above-mentioned hard conating is not particularly limited, from the scratch resistance of transparent resin lamilate of the invention or resistance to It can be usually 1 μm or more from the perspective of scratch resistance, preferably 5 μm or more, more preferably 10 μm or more, further preferably It is 20 μm or more.In addition, the thickness of above-mentioned hard conating from the machining adaptability of transparent resin lamilate of the invention, from It can be preferably 100 μm hereinafter, more preferably 50 μm or less from the perspective of rationality.
3. the layer of transparent resin sheet
The layer of above-mentioned transparent resin sheet makes from using transparent resin lamilate of the invention as instead of the material of glass Purpose is set out, and there is no restriction other than with high transparency and no coloring, and arbitrary transparent resin can be used Piece.
As transparent resin sheet, such as the cellulose esters system resin such as can enumerate triacetyl cellulose；Poly terephthalic acid second The polyester based resins such as diol ester；The ring-type hydrocarbon system resin such as vinyl norbornene copolymer；Polymethyl methacrylate, poly- methyl The acrylic resins such as ethyl acrylate；Poly- (methyl) acrylimide system resin；Aromatic polycarbonate system resin；Polypropylene, The polyolefin-based resins such as 4- methyl pentene -1；Polyamide resin；Polyacrylate system resin；Polymer-type carbamic acid Ester acrylic ester resin；And the thin slices such as polyimides system resins.Transparent resin sheet comprising no Extendible flake, uniaxial extension piece and Twin shaft Extendible flake.In addition, including their one kind or two or more laminated sheet.
As the preferred example of transparent resin sheet, following person can be enumerated.
(a1) poly- (methyl) acrylimide series resin sheet；
(a2) acrylic resin piece；
(a3) aromatic polycarbonate series resin sheet；
(a4) polyester based resin piece；
(a5) any one kind or two or more laminated sheet of above-mentioned transparent resin sheet a1-a4.
Above-mentioned (a1) poly- (methyl) acrylimide series resin sheet is by containing poly- (methyl) acrylimide as principal component It is that the resin of resin is formed by thin slice." principal component " therein refers to usual 80 mass % or more, preferably 90 mass % with On.
Above-mentioned poly- (methyl) acrylimide system resin is the high transparency, high surface hardness, height in acrylic resin It is introduced directly into the heat resistance of polyimides system resins or the feature of excellent in dimensional stability in the feature of rigidity, improves coloring At the thermoplastic resin of faint yellow to russet disadvantage.Poly- (methyl) acrylimide system resin is for example disclosed in Japanese spy In table 2011-519999 bulletin.In the present specification, poly- (methyl) acrylimide refers to polyacrylimide or poly- first Base acrylimide.
As above-mentioned poly- (methyl) acrylimide system resin, from using transparent resin lamilate as the material for replacing glass Material carry out using purpose set out, there is no restriction other than with high transparency, and arbitrary known poly- (methyl) can be used Acrylimide system resin.
As the preferred person of above-mentioned poly- (methyl) acrylimide system resin, yellow index can be enumerated (according to JIS K7105:1981 is measured using the colorimeter " SolidSpec-3700 (trade name) " of Shimadzu Scisakusho Ltd) be 3 or less persons.The yellow index of poly- (methyl) acrylimide system resin is more preferably 2 hereinafter, further preferably 1 or less.
In addition, from the viewpoint of squeezing out the stability of load or molten sheet, it is sub- as preferred poly- (methyl) acryloyl Amine system resin, can enumerate melt flow rate (MFR) (according to ISO1133, measuring under conditions of 260 DEG C, 98.07N) is 0.1- 20g/10 minute person.The melt flow rate (MFR) of poly- (methyl) acrylimide system resin is more preferably 0.5-10g/10 minutes.
In turn, the glass transition temperature of poly- (methyl) acrylimide system resin is preferred from the viewpoint of heat resistance It is 150 DEG C or more.Glass transition temperature is more preferably 170 DEG C or more.
In addition, above-mentioned poly- (methyl) as long as do not violate the object of the invention in acrylimide system resin, it can also be according to need It will be further containing other additives.The type and use level of these any ingredients and the activity for being used for above-mentioned first aspect Ingredient used in energy line curing resin composition is identical.
As the commercially available example of above-mentioned poly- (methyl) acrylimide system resin, with the active energy for above-mentioned first aspect It is same to measure line hardening resin composition institute user, " PLEXIMID TT70 (trade name) " of Evonik company can be enumerated Deng.
Above-mentioned (a2) acrylic resin piece is by containing polymethyl methacrylate, polymethyl as principal component The resin of the acrylic resins such as acetoacetic ester is formed by thin slice." principal component " therein typically refers to 50 mass % or more, excellent Select 60 mass % or more.
As above-mentioned acrylic resin, such as can enumerate containing poly- (methyl) methyl acrylate, poly- (methyl) acrylic acid Ethyl ester, poly- (methyl) propyl acrylate, poly- (methyl) butyl acrylate, (methyl) methyl acrylate (methyl) acrylic acid fourth (methyl) the acrylate (co) polymers such as ester copolymer, (methyl) ethyl acrylate (methyl) butyl acrylate copolymer； Ethylene (methyl) methyl acrylate copolymer, styrene (methyl) methyl acrylate copolymer etc. contain (methyl) acrylic acid The one kind or two or more mixture and methacrylate styrene of the acrylic resins such as the copolymer of ester (Acry)/ Butadiene rubber graft copolymer, acrylonitrile styrene/butadiene rubber graft copolymer, acrylonitrile styrene/second Allyl alkene rubber graft copolymer, acrylonitrile styrene/acrylate graft copolymers, methacrylate/acrylic acid The core shells rubber (Core) such as ester rubber graft copolymer, methacrylate acrylonitrile nitrile/acrylate rubber graft copolymer One kind or two or more mixture resin combination.
Wherein, (methyl) acrylic acid refers to acrylic or methacrylic acid here.In addition, (co) polymer refers to polymerization Object or copolymer.
The match ratio of above-mentioned Acry and above-mentioned Core is when making 100 mass parts of total amount of the two, preferably Acry 50- 85 mass parts: Core 50-15 mass parts, more preferably Acry 60-75 mass parts: Core 40-25 mass parts.
In addition, can be enumerated above-mentioned as any other ingredient that can contain in above-mentioned acrylic resin composition Thermoplastic resin other than Acry or above-mentioned Core；Pigment, inorganic filler, organic filler, resin filler；Lubricant, Additives such as antioxidant, weatherability stabilizer, heat stabilizer, release agent, antistatic agent, core agent and surfactant etc..This The use level of a little any ingredients is usually in 100 mass parts of total amount for making Acry and Core, and usually 25 below the mass, Preferably 0.01-10 mass parts or so.
Above-mentioned (a3) aromatic polycarbonate series resin sheet is by the resin as principal component system containing aromatic polycarbonate resin It is formed by thin slice." principal component " therein refers to usual 70 mass % or more, preferably 90 mass % or more.
As above-mentioned aromatic polycarbonate system resin, can be used for example bis- by bisphenol-A, dimethyl bisphenol A, 1,1- The interfacial polymerization of the aromatic dihydroxy compounds such as (4- hydroxy phenyl) -3,3,5- trimethyl-cyclohexane and phosgene is obtained Polymer；Pass through the aromatics dihydroxies such as bis- (4- the hydroxy phenyl) -3,3,5- trimethyl-cyclohexanes of bisphenol-A, dimethyl bisphenol A, 1,1- The aromatic polycarbonates system such as ester exchange reaction polymer obtained of the carbonic diesters such as based compound and diphenyl carbonate tree The one kind or two or more mixture of rouge.
As the preferred any ingredient that can contain in above-mentioned aromatic polycarbonate system resin, core shell rubber can be enumerated.When When making 100 mass parts of total amount of aromatic polycarbonate system resin and core shell rubber, by with 0-30 mass parts (the poly- carbon of aromatics Acid esters system resin 100-70 mass parts), the preferably amount of 0-10 mass parts (aromatic polycarbonate system resin 100-90 mass parts) Using core shell rubber, can be further improved above-mentioned (a3) aromatic polycarbonate series resin sheet resistance to machinability or resistance to punching Hitting property.
As above-mentioned core shell rubber, such as methacrylate styrene/butadiene rubbers graft copolymerization can be enumerated Object, acrylonitrile styrene/butadiene rubber graft copolymer, acrylonitrile styrene/ethylene propylene rubber graft copolymerization Object, acrylonitrile styrene/acrylate graft copolymers, methacrylate/acrylate rubber graft copolymer, first The core shells rubber such as base acrylate acrylonitrile/acrylate rubber graft copolymer.As core shell rubber, this can be used The mixture of a little one kind or two or more core shell rubber.
As long as, can also further basis in addition, do not violate the object of the invention in above-mentioned aromatic polycarbonate system resin It needs containing the thermoplastic resin other than aromatic polycarbonate system resin or core shell rubber；Pigment, organic is filled out inorganic filler Fill agent, resin filler；Lubricant, antioxidant, weatherability stabilizer, heat stabilizer, release agent, antistatic agent and surface Additives such as activating agent etc..The use level of these any ingredients usually makes aromatic polycarbonate system resin and core shell rubber It is 0.01-10 mass parts or so when total amount is 100 mass parts.
Above-mentioned (a4) polyester based resin piece is by containing the polyester based resins such as polyethylene terephthalate as principal component Resin be formed by thin slice." principal component " therein refers to usual 80 mass % or more, preferably 90 mass % or more.This is poly- Ester series resin sheet includes no Extendible flake, uniaxial extension piece and twin shaft Extendible flake.In addition, the polyester based resin piece includes their 1 Kind or laminated sheet of more than two kinds.
Above-mentioned (a4) polyester based resin piece is preferably by containing amorphism or low-crystalline aromatic polyester system tree as principal component The resin of rouge is formed by thin slice." principal component " therein refers to usual 80 mass % or more, preferably 90 mass % or more.
As above-mentioned amorphism or low-crystalline aromatic polyester system resin, such as terephthalic acid (TPA), isophthalic diformazan can be enumerated The aromatic polycarboxylic acids such as acid, phthalic acid, naphthalene dicarboxylic acids ingredient and ethylene glycol, diethylene glycol (DEG), neopentyl glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 3- methyl-1,5- pentanediol, 2- methyl-1,3-propanediol, 1,4- ring The polyester based copolymer of the polyol components such as hexane dimethanol.More specifically, the 100 moles of % of summation for making monomer, can Enumerate terephthalic acid (TPA) 50 moles of % and 30-40 moles of % of ethylene glycol, 10-20 moles of % of 1,4 cyclohexane dimethanol is constituted Glycol modification polyethylene terephthalate (PETG)；16-21 moles of 50 moles of % of terephthalic acid (TPA), ethylene glycol % and Two methylene ester of glycol modification poly terephthalic acid Asia cyclohexyl that 29-34 moles of % of 1,4 cyclohexane dimethanol is constituted (PCTG)；0.5-25 moles of 25-49.5 moles of % of terephthalic acid (TPA), M-phthalic acid % and 1,4- cyclohexanedimethanol 50 rub Modified two methylene ester (PCTA) of poly terephthalic acid Asia cyclohexyl of the acid that your % is constituted；30-45 moles of % of terephthalic acid (TPA), 35-48 moles of % of 5-20 moles of % of M-phthalic acid and ethylene glycol, 2-15 moles of % of neopentyl glycol, diethylene glycol (DEG) rub less than 1 1 kind or 2 kinds of sour modification and glycol modification polyethylene terephthalate etc. that your less than 1 mole %, bisphenol-A % are constituted Above mixture.
In this specification, the Diamond DSC type differential scanning calorimetry of P Co., Ltd. erkinElmer will be used, with Sample is kept after five minutes, to be cooled to -50 DEG C with 20 DEG C/min of cooling rate at 320 DEG C, 5 points are kept at -50 DEG C Zhong Hou, second melting curve (the last liter measured with the temperature program(me) that 20 DEG C/min of heating rate is heated to 320 DEG C The melting curve measured during temperature) melting heat be that 10J/g polyester below is defined as amorphism, more than 10J/g and 60J/g polyester below is defined as low-crystalline.
As long as not violating the purpose of the present invention in above-mentioned polyester based resin, can according to need containing other compositions.Make For any ingredient that can contain, the thermoplastic resin other than polyester based resin can be enumerated；Pigment, organic is filled out inorganic filler Fill agent, resin filler；Lubricant, antioxidant, weatherability stabilizer, heat stabilizer, release agent, antistatic agent and surface Additives such as activating agent etc..The use level of these any ingredients is when making 100 mass parts of polyester based resin, usually 25 matter Part is measured hereinafter, preferably 0.01-10 mass parts or so.
As the preferred any ingredient contained in above-mentioned polyester based resin, core shell rubber can be enumerated.By using core shell The impact resistance of above-mentioned (a4) polyester based resin piece can be improved in rubber.
As above-mentioned core shell rubber, such as methacrylate styrene/butadiene rubbers graft copolymerization can be enumerated Object, acrylonitrile styrene/butadiene rubber graft copolymer, acrylonitrile styrene/ethylene propylene rubber graft copolymerization Object, acrylonitrile styrene/acrylate graft copolymers, methacrylate/acrylate rubber graft copolymer, first The one kind or two or more mixture of the core shells rubber such as base acrylate acrylonitrile/acrylate rubber graft copolymer.Make For core shell rubber, their one kind or two or more mixture can be used.
The use level of above-mentioned core shell rubber is excellent in order to improve impact resistance when making 100 mass parts of polyester based resin It is selected as 0.5 mass parts or more.And in order to keep the transparency, the use level of core shell rubber is preferably 5 below the mass, more preferably Below the mass for 3.
For the one kind or two or more laminated sheet of transparent resin sheet a1-a4 above-mentioned for above-mentioned (a5), laminated orders It is not particularly limited, most preferably directly laminated first poly- (methyl) acrylimide resin in order；The poly- carbon of aromatics Acid esters resin；The laminated sheet of second poly- (methyl) acrylimide resin.
At this point, the preferably first poly- (methyl) acrylimide resin and second gathers from the viewpoint of resistance to bend(ing) (methyl) acrylimide resin is essentially identical thickness.In addition, the first poly- (methyl) acrylimide resin It may be the same or different with the second poly- (methyl) acrylimide resin, but preferably resin properties having the same, it is more excellent Choosing is the same batch of same rank.
Above-mentioned (a5) above-mentioned transparent resin sheet a1-a4's appoints one kind or two or more laminated sheet that can for example obtain as follows: making With any co-extrusion devices such as feeding block mode, branch manifold mode and lamination modes, progress co-extrusion is constituted according to required layer is become It is film-made out；Or using arbitrary film forming apparatus obtain above-mentioned transparent resin sheet a1-a4 appoint it is one kind or two or more after, according to Reach required layer to constitute to their progress heat laminations or dry lamination；Or it is obtained using arbitrary film forming apparatus above-mentioned transparent After wantonly a kind of resin sheet a1-a4, is constituted using the thin slice as substrate, according to becoming required layer and carry out extrusion lamination, to obtain ?.
Manufacturing method for obtaining above-mentioned transparent resin sheet is not particularly limited, such as can be enumerated including following process Method: (P) continuously squeezes out the work of the molten sheet of transparent resin from T die head using having the device of extruder and T die head Sequence；(Q) in the first specular surface body for being rotated or being recycled and rotated or the second specular surface body for recycling between in supply investment The process stating the molten sheet of transparent resin and being squeezed.
Any known person can be used in T die head as above-mentioned operation (P).As T die head, such as manifold mould can be enumerated Head, fish tail coventry type die head coventry and hanger-style die etc..
Any known person can be used in extruder as above-mentioned operation (P).As extruder, such as single shaft can be enumerated Extruder, equidirectional rotation biaxial extruder and different direction rotate biaxial extruder etc..
In addition, the deterioration in order to inhibit transparent resin, is also one of preferred method to nitrogen purging is carried out in extruder.
In turn, preferably it is dried before transparent resin to be supplied to film.It is also preferable in drying machine Transparent resin is fed directly to extruder from drying machine to put into.Additionally, it is preferred that (usually propeller in an extruder The metering region of front end) setting vacuum ventilation mouth.
As the first specular surface body of above-mentioned operation (Q), can be used and the above-mentioned operation that illustrated about first aspect (B) or (B ') identical person.
Be not in order to theoretically be constrained, but can consider by above-mentioned film-forming method obtain the transparency, surface The reason of transparent resin sheet of flatness and excellent appearance, is as follows: by utilizing the first specular surface body and the second specular surface body to transparent The molten sheet of resin is squeezed, and the smooth surface state of the height of the first specular surface body and the second specular surface body is transferred on film, is repaired The just defective works such as die head striped.
In order to carry out the transfer of above-mentioned surface state well, the surface temperature of the first specular surface body is preferably 80 DEG C or more, more Preferably 100 DEG C or more.And the adjoint bad order (removing trace) with the removing of the first specular surface body is presented in piece in order to prevent, The surface temperature of first specular surface body is preferably 200 DEG C hereinafter, more preferably 160 DEG C or less.
In order to carry out the transfer of above-mentioned surface state well, the surface temperature of the second specular surface body is preferably 20 DEG C or more, more Preferably 60 DEG C or more.And the adjoint bad order (removing trace) with the removing of the second specular surface body is presented in piece in order to prevent, the The surface temperature of two specular surface bodies is preferably 200 DEG C hereinafter, more preferably 160 DEG C or less.
Additionally, it is preferred that keeping the surface temperature of the first specular surface body also higher than the surface temperature of the second specular surface body.This is because will Film is embraced in the first specular surface body, is sent in next transfer roller.
In addition, when forming above-mentioned hard conating, in the hard conating forming face or two for the above-mentioned transparent resin sheet for becoming substrate Face can also implement discharge treatment or cementation coating is formed etc. easy bonding to improve the adhesion strength with hard conating in advance Processing.
The thickness of above-mentioned transparent resin sheet is not particularly limited, and be can according to need and is become arbitrary thickness.It will be of the invention Transparent resin lamilate further other substrates are laminated in use, from treatability with polycarbonate plate or acrylic panel etc. Viewpoint is set out, and the thickness of above-mentioned transparent resin sheet can be usually 20 μm or more, and preferably 50 μm or more.In addition, from economy From the perspective of, the thickness of above-mentioned transparent resin sheet can be usually 250 μm hereinafter, preferably 150 μm or less.
Using transparent resin lamilate of the invention as replace vehicle glass pane or building glass pane component into Row is in use, the thickness of above-mentioned transparent resin sheet can be usually 1mm or more, preferably from the viewpoint of keeping rigidity 1.5mm or more, more preferably 2mm or more.In addition, from the viewpoint of the lightweight requirements of counterpart member, above-mentioned transparent resin The thickness of piece can be usually 6mm hereinafter, preferably 4mm is hereinafter, more preferably 3mm or less.
The full light transmittance of above-mentioned transparent resin sheet (according to JIS K7361-1:1997, uses Japanese electric color industry strain The haze meter " NDH2000 " (trade name) of formula commercial firm measures) it is preferably 80% or more, more preferably 85% or more, it is further excellent It is selected as 90% or more.The full light transmittance the high the more preferred.
In addition, the mist degree of above-mentioned transparent resin sheet (according to JIS K7136:2000, uses Japanese electric color industry strain formula meeting The haze meter " NDH2000 " (trade name) of society measures) it is preferably 5% hereinafter, more preferably 3% hereinafter, further preferably 2% or less.The mist degree the low the more preferred.
In turn, the yellow index of above-mentioned transparent resin sheet (according to JIS K7105:1981, uses Shimadzu Seisakusho Ltd.'s public affairs Department system colorimeter " SolidSpec-3700 " (trade name) measurement) be preferably 3 hereinafter, more preferably 2 hereinafter, further it is excellent It is selected as 1 or less.The yellow index the low the more preferred.
4. the preferred characteristics of transparent resin lamilate
Transparent resin lamilate of the invention from as replace glass material carry out using purpose, it is necessary to It colours with high transparency and not.
For this purpose, same as above-mentioned transparent resin sheet, the full light transmittance of transparent resin lamilate of the invention (according to JIS K7361-1:1997, being measured using the haze meter " NDH2000 " (trade name) of Nippon Denshoku Industries Co., Ltd.) Preferably 80% or more, more preferably 85% or more, further preferably 90% or more.The full light transmittance the high the more preferred.
In addition, the mist degree of transparent resin lamilate of the invention (according to JIS K7136:2000, uses Japanese electric color work The haze meter " NDH2000 " (trade name) of industry Co., Ltd. measures) it is preferably 5% hereinafter, more preferably 3% hereinafter, further Preferably 2% or less.The mist degree the low the more preferred.
In turn, the yellow index of transparent resin lamilate of the invention (according to JIS K7105:1981, uses Shimadzu The colorimeter " SolidSpec-3700 " (trade name) of manufacturing company measures) be preferably 3 hereinafter, more preferably 2 hereinafter, Further preferably 1 or less.The yellow index the low the more preferred.
Embodiment
Illustrate the present invention following with embodiment, but the present invention is not limited to these.
The measurement/evaluation method of physical property
(1) full light transmittance
According to JIS K7136-1:1997, haze meter " NDH2000 " (commodity of Nippon Denshoku Industries Co., Ltd. are used Name) the full light transmittance of measurement.
(2) mist degree
According to JIS K7136:2000, the haze meter " NDH2000 " (trade name) of Nippon Denshoku Industries Co., Ltd. is used Measure mist degree.
(3) yellow index (YI)
According to JIS K7105:1981, colorimeter " SolidSpec-3700 " (commodity of Shimadzu Seisakusho Ltd.'s corporation are used Name) measurement yellow index.
(4) water contact angle
Using the automatic contact angle meter " DSA20 " (trade name) of KRUSS company, counted using by the width and height of water droplet The method (referring to JIS R3257:1999) of calculation is to the touch surface side hard conating face of hard conating laminate film or transparent resin lamilate Hard conating face be measured.
(5) marresistance (water contact angle after wiping)
By the size to indulge 150mm, horizontal 50mm, according to the machine direction of hard conating laminate film or transparent resin lamilate It is placed in the vibration testing machine of JIS L0849 for the test film that the longitudinal direction of test film is acquired, so that hard conating is laminated Touch surface side hard conating face or the hard conating face of transparent resin lamilate of film become surface.In the friction side for learning vibration testing machine The stainless steel plate that the gauze (1 gauze of medical type of this Industry Co., Ltd of river) being overlapped by 4 covers is installed (vertical on son 10mm, horizontal 10mm, thickness 1mm), by being installed in the way of face is in contact with test film in length and breadth for the stainless steel plate.It places 350g loading, it is laminated to the hard conating of test film under conditions of 1 round-trip/second of speed with the moving distance 60mm for the terminal that rubs The touch surface side hard conating face of film or the hard conating face of transparent resin lamilate wipe 2 Wan Cihou back and forth, according to above-mentioned (4) Method measures the water contact angle of the wiping position.In addition, being judged as that marresistance is good if water contact angle is 100 degree or more It is good.In addition, also having carried out required round-trip number being altered to 10,000 when the water contact angle after 20,000 times round-trip is less than 100 degree 5000 times and 10,000 times measurements, are evaluated using following standard.
◎ (very good): even round-trip 2 Wan Cihou of number, water contact angle is also 100 degree or more.
Zero (good): after round-trip number 10,000 5 thousand times, water contact angle is 100 degree or more, but less than 100 degree after 20,000 times.
△ (slightly bad): 1 Wan Cihou of round-trip number, water contact angle is 100 degree or more, but less than 100 after 10,000 5 thousand times Degree.
× (bad): 1 Wan Cihou of round-trip number, water contact angle is less than 100 degree.
(6) finger sliding property
The touch surface side hard conating face of hard conating laminate film drawn into using index finger it is up and down or round, using being The no impression that can be drawn as being wanted is evaluated.Test carries out respectively for 10, will be as drawn with thinking Situation is calculated as 2 points, and substantially as the case where drawn with thinking is calculated as 1 point, finger blocks the not feelings as drawn with thinking Condition is calculated as 0 point, calculates each one score, is evaluated using following standard.
◎ (very good): 16-20 points
△ (slightly bad): 10-15 point
× (bad): 0-9 points
(7) the finger sliding property after wiping
In addition to using the hard conating laminate film of 2 Wan Cihou of round-trip wiping as sample other than, with above-mentioned (6) finger sliding property It is carried out similarly test, evaluation.
(8) marresistance
Become surface according to the touch surface side hard conating face of hard conating laminate film or the hard conating face of transparent resin lamilate Mode, by hard conating laminate film or transparent resin lamilate be placed on JIS L0849 vibration testing machine in.Then, it is learning After the steel wool for installing #0000 on the friction terminal of vibration testing machine, 500g loading is placed, the surface of test film is wiped back and forth 100 times.Above-mentioned surface is visually observed, is evaluated using standard below.
Equally, the printing surface side hard conating face of hard conating laminate film has also been carried out testing/evaluating.Wherein, it is recorded in table Touch the result/printing surface side result of surface side.
◎ (very good): there is no scar.
Zero (good): there is the scar of 1-5 root.
△ (slightly bad): there is the scar of 6-10 root.
× (bad): there are 11 or more scars.
(9) linear expansion coefficient
Linear expansion coefficient is measured according to JIS K7197:1991.Use the heat engine of Seiko Instruments Co., Ltd. Tool analytical equipment (TMA) " EXSTAR6000 " (trade name).Test film is the size of vertical 20mm, horizontal 10mm, according to the machine of film The longitudinal direction that direction (MD) becomes test film is acquired.The status adjustment of test film is in 23 DEG C ± 2 DEG C of temperature, relatively wet Lower 24 hours of degree 50 ± 5% measures the shape under maximum temperature to measure as the purpose of the dimensional stability of the physics value of film State adjusting does not carry out.Distance is 10mm between clip, and temperature program(me) is after being kept for 3 minutes at 20 DEG C of temperature, with heating rate 5 DEG C/min it is warming up to 270 DEG C of temperature of program.Linear expansion coefficient is by gained assay-temperatures leaf length curve, with low temperature side 30 DEG C of temperature, 250 DEG C of high temperature side temperature calculated.
(10) minimum bending radius
It is reference with the bending forming (B method) of JIS-K6902:2007, in 23 DEG C ± 2 DEG C of temperature, relative humidity 50 The test film that 24 hours status adjustments have been carried out under ± 5%, at 23 DEG C ± 2 DEG C of flexure temperature, bending line and hard coat layers Close the machine direction direction at right angle of film, be bent according to the touch surface side hard conating of hard conating laminate film as outside, The mode for forming curved surface carries out.By the front portion of the radius reckling of front portion in the forming jig that crackle does not occur half Diameter is as minimum bending radius.It is somebody's turn to do " front portion " and refers to the forming with the B method of 18.2 defineds of JIS K6902:2007 The related identical term of fixture.
(11) machinability (state of curve-like machining line)
Using the milling processing machine carried out automatically controlling by computer, radius 0.5mm is set in hard conating laminate film Circular cutting hole and radius 0.1mm circular cutting hole.The grinder used at this time is that the front end geometry of point of a knife is round 4 swords of cemented carbide, the notched grinder of cylinder ball-type, cutter diameter are properly selected according to Working position.Then, for For the cutting hole of radius 0.5mm, cuts it end face and carry out visual or (100 times) of microscope observations, utilize mark below Standard is evaluated.Equally, it for the cutting hole of radius 0.1mm, cuts it end face and carries out visual or (100 times) of microscope sights It examines, is evaluated using standard below.The former result-the latter result is described in table in order.
◎ (very good): even micro- sem observation also has no crackle, flash.
Zero (good): even micro- sem observation also has no crackle.But see flash.
△ (slightly bad): crackle is had no under visually.But visible flash under micro- sem observation.
× (bad): crackle is even visually also had no.
(12) surface smoothness (appearance)
Change the incidence angle irradiation hard conating laminate film of the light of fluorescent lamp or the table of transparent resin lamilate on one side variously Face (two faces), is visually observed on one side, is evaluated using following standard.
◎ (very good): surface does not rise and fall or scar.It is observed in front of even taking through light, is not also had Dim sense.
Zero (good): when being observed in front of taking through light, there is the position of slightly dim sense.
△ (slightly bad): when being observed in front of taking, the slightly visible fluctuating in surface or scar.In addition, having dim Sense.
× (bad): the visible multiple fluctuatings in surface or scar.In addition, there is apparent dim sense.
(13) pencil hardness
According to JIS K5600-5-4, the pencil " UNI of Mitsubishi Pencil K. K is used under conditions of 750g loading (trade name) " measures pencil hardness.Wherein, it is described for hard conating laminate film, in table and touches surface side measured value/print Brush finish side measured value.
(14) weatherability
Using the weathering tester of daylight carbon arc lamp-type as defined in JIS B7753:2007, in JIS A5759:2008 The condition of table 10 (test film is the size of vertical 125mm, horizontal 50mm, becomes examination according to the machine direction of transparent resin lamilate The longitudinal direction for testing piece is acquired, directly use, do not carry out the attaching on glass) under carry out 2000 hours promotion it is weather-proof Property test.The N number of test is 3, the appearances such as does not expand, cracks and peel off in transparent resin lamilate in total Test The case where variation is qualified (be ◎ in table), in addition to this case where for unqualified (being in table ×).
(15) impact resistance
In cuboid metal clamps formed by each wall surface of front panel, backplate and side panel, upper opening Simultaneously fixed transparent resin lamilate is arranged in (vertical 1100mm, horizontal 900mm, high 200mm) so that hard conating face be above, will be above-mentioned The opening portion of fixture fully covers.Then, by diameter 100mm, quality 4.11Kg metal ball from transparent resin lamilate Top 3000mm height respectively falls to the one side being imprinted near the portion centers of covering transparent resin lamilate opening portion respectively It is total to fall 3 times 1 time on the vertex of the equilateral triangle of 130mm.The N number of test is 3, as long as total Test metal ball does not penetrate through Transparent resin lamilate be then qualified (be ◎ in table), in addition to this case where for unqualified (being in table ×).
The raw material used
(A) multifunctional (methyl) acrylate:
(A-1) dipentaerythritol hexaacrylate (6 function)
(A-2) ethoxylated trimethylolpropane acrylate (3 function)
(B) with the compound of alkoxysilyl and (methyl) acryloyl group:
(B-1) " SHIN-ETSU HANTOTAI Silicone KR-513 " (trade name of Shin-Etsu Chemial Co., Ltd；R: methoxyl group, R ': Acryloyl group, R ": methyl)
(B-2) " SHIN-ETSU HANTOTAI Silicone X-40-2655A " (trade name of Shin-Etsu Chemial Co., Ltd；R: methoxy Base, R ': methylacryloyl, R ": methyl)
(B ') compares ingredient:
" SHIN-ETSU HANTOTAI Silicone KBM-403 " (trade name of (B ' -1) Shin-Etsu Chemial Co., Ltd；With alkoxy Silicyl and epoxy group do not have the compound of (methyl) acryloyl group)
" SHIN-ETSU HANTOTAI Silicone KBM-903 " (trade name of (B ' -2) Shin-Etsu Chemial Co., Ltd；With alkoxy Silicyl and amino do not have the compound of (methyl) acryloyl group)
(C) organic titanium:
(C-1) the isopropoxy octamethylene glycolic titanium " TOG " (trade name) of Tso Tat Co., Ltd., Japan
(C-2) four (2- ethyl hexyl oxy) titaniums " TOT (trade name) " of Tso Tat Co., Ltd., Japan
(C-3) bis- (levulinic ketone group) titaniums " T-50 " (trade name) of the diisopropoxy of Tso Tat Co., Ltd., Japan
(C ') compares ingredient:
Four n-propoxyzirconiums " ZAA " (trade name) of (C ' -1) Tso Tat Co., Ltd., Japan
(D) particle of average grain diameter 1-300nm:
(D-1) silicon dioxide microparticle of average grain diameter 20nm
(E) hydrophobing agent:
(E-1) perfluoroalkyl polyether system hydrophobing agent " KY-1203 " (commodity containing acryloyl group of Shin-Etsu Chemial Co., Ltd Name；20 mass % of solid content)
(E-2) perfluoroalkyl polyether system hydrophobing agent " FOMBLIN MT70 " (trade name containing methylacryloyl of Solvay society；Gu 70 mass % of body content)
(E-3) the perfluoroalkyl polyether system hydrophobing agent " Megafac RS-91 " (trade name) containing acryloyl group of Dainippon Ink Chemicals
Any other ingredient:
(F-1) the phenyl ketone system Photoepolymerizationinitiater initiater (1- hydroxycyclohexylphenylketone) of Shuan Bangbao industry joint stock company limited " SB-PI714 " (trade name)
(F-2) 1- methoxy-2-propanol
(F-3) surface conditioner " BYK-399 " (trade name) of BYK Japan Co., Ltd.
(F-4) hydroxy-ketone system Photoepolymerizationinitiater initiater (Alpha-hydroxy alkyl acyl benzene) " Irgacure 127 " (commodity of BASF society Name)
I. the hard conating laminate film and its comparative example of the active energy line curing resin composition of first aspect have been used
Poly- (methyl) acryloyl for preparing (α -1) Evonik company as (α) poly- (methyl) acrylimide system resin is sub- Amine " PLEXIMID TT70 " (trade name) and as (β) aromatic polycarbonate system's resin prepare (β -1) live change Styron The aromatic polycarbonate " Calibre 301-4 " (trade name) of Polycarbonate Co., Ltd..
Coating is used in addition, being formed as (γ) printing surface side hard conating, with above-mentioned A-1 be 65 mass parts, above-mentioned A-2 is 35 mass parts, above-mentioned B-1 are 1.4 mass parts, above-mentioned C-1 is 0.7 mass parts, above-mentioned D-1 is 35 mass parts, above-mentioned F-1 is 5.3 mass parts, above-mentioned F-2 are 95 mass parts and above-mentioned F-3 is the cooperation ratio of components progress mixed/stirred of 0.5 mass, modulation Coating (γ -1).
Such as a variety of (P) transparent resin films of modulated.
(p-1) the coextrusion film forming apparatus that the composition of concept map is shown using Fig. 1, makes above-mentioned (α -1) using extruder 1 For two outer layers (2 layers of 1 layer of α and α) of transparent multilayer film, above-mentioned (β -1) is set to be the middle layer of transparent multilayer film using extruder 2 (β layers) directly laminated in order will have 1 layer of α；β layers；The fused film 4 for the transparent multilayer film that 2 layers of α is from 2 kinds of 3 layers of branch manifold modes Coextrusion T die head 3 continuously squeeze out.The fused film 4 is supplied into investment rotation in such a way that 1 layer of α is 5 side of mirror roller Mirror roller 5 and hang over it is in a pair of of belt roller 7, along mirror roller 5 outer peripheral surface recycle mirror surface band 6 between, squeezed, obtained The transparent multilayer film that total thickness is 250 μm, 1 layer of α of thickness is 80 μm, β layers of thickness is 90 μm, 2 layers of α of thickness is 80 μm. At this point, imposing a condition are as follows: as the drying temperature before film, (α -1) is 150 DEG C, and (β -1) is 100 DEG C；The setting of extruder 1 C1/C2/C3/C4/C5/AD=260/290-290 DEG C of temperature；The set temperature C1/C2/C3/C4/C5/C6/AD=of extruder 2 260/280/280/260-260/270℃；Extruder 1,2 carries out nitrogen purging, uses vacuum ventilation mouth；T die head 3 is set Determine 300 DEG C of temperature, die gap 0.5mm；130 DEG C of the set temperature of mirror roller 5；120 DEG C of the set temperature of mirror surface band 6 squeezes 1.4MPa；Hauling speed 6.5m/ minutes.
(p-2) above-mentioned (α -1) is utilized, (the W screw thread of L/D=29, CR=1.86 is installed using equipment 50mm extruder Screw rod)；The T die head of the wide 680mm of die head；It is squeezed with utilization mirror roller (the first specular surface body) and mirror surface band (the second specular surface body) The device of the wrapping machine of the function of fused film obtains 250 μm of thickness of film.At this point, imposing a condition are as follows: the setting temperature of extruder C1/C2/C3/AD=280/300/320/320 DEG C of degree；320 DEG C of the set temperature of T die head；The die gap 0.5mm of T die head； 140 DEG C of the set temperature of mirror roller；120 DEG C of the set temperature of mirror surface band；The extruding 1.4MPa of mirror surface band；Hauling speed 5.6m/ Minute.
(p-3) twin shaft of Mitsubishi Plastics Inc extends PET series film " Diafoil " (quotient The name of an article；250 μm of thickness)
(p-4) acrylic resin film " Technolloy S001G " (trade name of Sumitomo Chemical Co；Thickness 250μm)
(p-5) above-mentioned (β -1) is utilized, (the W screw thread of L/D=29, CR=1.86 is installed using equipment 50mm extruder Screw rod)；The T die head of the wide 680mm of die head；It is squeezed with utilization mirror roller (the first specular surface body) and mirror surface band (the second specular surface body) The device of the wrapping machine of the function of fused film obtains 250 μm of thickness of film.At this point, imposing a condition are as follows: the setting temperature of extruder C1/C2/C3/AD=280/300/320/320 DEG C of degree；320 DEG C of the set temperature of T die head；The die gap 0.5mm of T die head； 140 DEG C of the set temperature of mirror roller；120 DEG C of the set temperature of mirror surface band；The extruding 1.4MPa of mirror surface band；Hauling speed 5.6m/ Minute.
Embodiment 1
To the two sides of the transparent resin film of above-mentioned p-1 in treating capacity 167Wmin/m2(discharge energy 500W, electric discharge electricity The length 1m, linear velocity 3m/min of pole) under conditions of carry out Corona discharge Treatment.Two sides is that wetting index is 64mN/m.It connects , on 1 layer of side α of transparent resin film, as surface side hard conating formation coating is touched, use the covering with paint of die head mode With the coating for being combined into (mass parts) shown in device coating table 1, so that thickness reaches 25 μm after solidification；In transparent resin film On the face of the 2 layers of side α, using the coating device of die head mode, above-mentioned γ-is coated with as printing surface side hard conating formation coating 1, so that thickness reaches 25 μm after solidification, obtain hard conating laminate film.Carry out above-mentioned test (1)-(13).Show the result in table 1。
Embodiment 2-14, comparative example 1-7
The change as shown in any of table 1-4, which touches, to be combined into matching for surface side hard conating formation coating, in addition to this entirely Portion similarly to Example 1, carries out the production transitivity evaluation of hard conating laminate film.It shows the result in either one or two of table 1-4.
Embodiment 15
To the two sides of the transparent resin film of above-mentioned p-2 in treating capacity 167Wmin/m2(discharge energy 500W, electric discharge electricity The length 1m, linear velocity 3m/min of pole) under conditions of carry out Corona discharge Treatment.Two sides is that wetting index is 63mN/m.It connects , on a face of transparent resin film, as surface side hard conating formation coating is touched, filled using the covering with paint of die head mode It sets with the coating being combined into shown in coating table 4, so that thickness reaches 25 μm after solidification；In another face of transparent resin film, Using the coating device of die head mode, it is coated with above-mentioned γ -1 as printing surface side hard conating formation coating, so that thick after solidification Degree reaches 25 μm, obtains hard conating laminate film.Carry out above-mentioned test (1)-(13).Show the result in table 4.
Embodiment 16
Die head is used as surface side hard conating formation coating is touched in a face of the transparent resin film of above-mentioned p-3 With the coating being combined into shown in the coating device coating table 4 of mode, so that thickness reaches 25 μm after solidification；In the another of the film A face is coated with above-mentioned γ -1 as printing surface side hard conating formation coating, so that solid using the coating device of die head mode Thickness reaches 25 μm after change, and it is fit to obtain hard coat layers.Carry out above-mentioned test (1)-(13).Show the result in table 4.Wherein, The test film contraction of test (9) related with linear expansion coefficient is very big, can not obtain measured value.
Embodiment 17
As transparent resin film, above-mentioned p-4 is used instead of above-mentioned p-3, in addition to this all similarly to Example 16, into The production transitivity of row hard conating laminate film is evaluated.Show the result in table 4.
Embodiment 18
As transparent resin film, above-mentioned p-5 is used instead of above-mentioned p-3, in addition to this all similarly to Example 16, into The production transitivity of row hard conating laminate film is evaluated.Show the result in table 4.
Embodiment 19
In addition to according to change shown in table 4 touch surface side hard conating formation coating with other than being combined into, all with implementation Example 1 is same, carries out the production transitivity evaluation of hard conating laminate film.Show the result in table 4.
Table 1
Table 2
Table 3
Table 4
Hard conating with the hard conating formed by the coating containing active energy line curing resin composition of the present invention The transparency, tone, marresistance (resistance to wiping and the woolliness of resistance to steel wire), surface hardness, flexing resistance and the appearance of laminate film It is excellent.On the other hand, the resistance to wiping of the hard conating laminate film of the comparative example 1 without ingredient C is very poor.Ingredient C is more than specified amount Comparative example 2 hard conating laminate film hue difference.Ingredient B is resistance to lower than the hard conating laminate film of the comparative example 3 of specified amount Wiping is poor.The hard conating laminate film that ingredient B ultrasound crosses the comparative example 4 of specified amount is difficult to show hydrophobicity.It is used instead of ingredient B With alkoxysilyl and epoxy group, there is no the hard conating laminate film of the comparative example 5 of the compound of (methyl) acryloyl group Resistance to wiping it is very poor.Using instead of ingredient B has alkoxysilyl and amino, does not have the change of (methyl) acryloyl group Close the hue difference of the hard conating laminate film of the comparative example 6 of object.The hard of the comparative example 7 of four n-propoxyzirconiums has been used instead of ingredient C The resistance to wiping of coating laminate film is poor.
II. the transparent resin lamilate and its comparative example of second aspect
Such as modulated a variety of (a) transparent resin sheet.
(a1-1) poly- (methyl) acrylimide series resin sheet:
Using poly- (methyl) the acrylimide system resin " PLEXIMID TT70 " (trade name) of Evonik company, use Fig. 2 shows the device for having extruder and T die head of the composition of concept map, and the molten sheet 9 of above-mentioned resin is continuous from T die head 8 Ground squeeze out, by above-mentioned molten sheet 9 supply investment rotation mirror roller 10 and hang over it is in a pair of of belt roller 12, along mirror roller 10 Outer peripheral surface circulation mirror surface band 11 between, squeezed, obtain with a thickness of 1mm transparent multilaminar piece.At this point, imposing a condition Are as follows: 140 DEG C of the set temperature of the first mirror roller, 120 DEG C of the set temperature of the second mirror roller, the resin temperature of T die head exit 300℃.The full light transmittance of gained transparent resin sheet is 92%, mist degree 1.0%, yellow index 0.6.
(a2-1) acrylic resin piece:
Using Sumitomo Chemical Company Ltd acrylic resin composition (70 mass parts of acrylic resin and The resin combination of 30 mass parts of acrylic acid series core shell rubber) " HT03Y " (trade name), using having extruder and T die head Device continuously squeezes out the molten sheet of above-mentioned resin from T die head, and above-mentioned molten sheet is supplied to the first mirror surface of investment rotation It between roller and the second mirror roller of rotation, is squeezed, obtains the transparent resin sheet with a thickness of 1mm.Setting condition at this time Are as follows: 100 DEG C of the set temperature of the first mirror roller, 80 DEG C of the set temperature of the second mirror roller, the resin temperature 300 of T die head exit ℃.The full light transmittance of gained transparent resin sheet is 86%, mist degree 2.7%, yellow index 0.7.
(a3-1) aromatic polycarbonate series resin sheet:
Use aromatic polycarbonate system resin " K-1300Y " (trade name) 99.5 mass parts of Teijin Chemicals, Ltd. With core shell rubber (methacrylate styrene/butadiene rubbers graft copolymer) " Kane of Co., Ltd. Kaneka The resin combination of 0.5 mass parts of Ace B-56 " (trade name), using the device for having extruder and T die head, by above-mentioned tree The molten sheet of rouge is continuously squeezed out from T die head, by above-mentioned molten sheet supply investment rotation the first mirror roller and rotation the It between two mirror rollers, is squeezed, obtains the transparent resin sheet with a thickness of 1mm.Setting condition at this time are as follows: the first mirror roller 140 DEG C of set temperature, 120 DEG C of the set temperature of the second mirror roller, 300 DEG C of the resin temperature of T die head exit.Gained is transparent The full light transmittance of resin sheet is 88%, mist degree 2.3%, yellow index 0.8.
(a4-1) polyester based resin piece:
Use the amorphism polyester based resin (PETG resin) " Cadence GS1 " of Eastman Chemical company (methacrylate styrene/butadiene rubbers connect the core shell rubber of (trade name) 99 mass parts and Co., Ltd. Kaneka Graft copolymer) " Kane Ace B-56 " (trade name) 1 mass parts resin combination, using having extruder and T die head Device continuously squeezes out the molten sheet of above-mentioned resin from T die head, and above-mentioned molten sheet is supplied to the first mirror surface of investment rotation It between roller and the second mirror roller of rotation, is squeezed, obtains the transparent resin sheet with a thickness of 1mm.Setting condition at this time Are as follows: 80 DEG C of the set temperature of the first mirror roller, 40 DEG C of the set temperature of the second mirror roller, the resin temperature 200 of T die head exit ℃.The full light transmittance of gained transparent resin sheet is 85%, mist degree 3.0%, yellow index 0.5.
(a5-1) laminated sheet 1:
It, will be with Evonik public affairs using the coextrusion film forming apparatus of 2 kinds of 3 layers of branch manifold modes for having extruder and T die head Poly- (methyl) the acrylimide system resin " PLEXIMID TT70 " (trade name) of department is used as two outer layers, to live to change Styron The melting layer of aromatic polycarbonate " Calibre 301-4 " (trade name) as middle layer of Polycarbonate Co., Ltd. It closes piece continuously to squeeze out from T die head, above-mentioned melting laminated sheet is supplied to the first mirror roller and the second of rotation of investment rotation Between mirror roller, squeezed, obtain overall thickness 1mm, the thickness 0.1mm of two outer layers, middle layer thickness 0.8mm it is transparent Resin sheet.Setting condition at this time are as follows: 140 DEG C of the set temperature of the first mirror roller, 120 DEG C of the set temperature of the second mirror roller, 300 DEG C of the resin temperature of T die head exit.The full light transmittance of gained transparent resin sheet is 91%, and mist degree 1.0% is yellow Chromaticity index is 0.7.
Embodiment 20
To the two sides of the transparent resin sheet of above-mentioned a1-1 in treating capacity 167Wmin/m2(discharge energy 500W, electric discharge electricity The length 1m, linear velocity 3m/min of pole) under conditions of carry out Corona discharge Treatment.Two sides is that wetting index is 64mN/m.It connects , on the two sides of the transparent resin sheet of above-mentioned a1-1, as hard conating formation coating, filled using the covering with paint of die head mode It sets with the coating for being combined into (mass parts) shown in coating table 1, so that thickness reaches 25 μm after solidification, it is laminated to obtain transparent resin Body.Carry out above-mentioned test (1)-(5), (8) and (12)~(15).Show the result in table 5.
Embodiment 21-33, comparative example 8-14
In addition to according to the change hard conating formation coating shown in any of table 5-8 with other than being combined into, all The production transitivity evaluation of transparent resin lamilate is carried out similarly to Example 20.It shows the result in either one or two of table 5-8. Comparative example 11 tests the marresistance of (5) (after wiping since the water contact angle (test (4)) at initial stage is less than 100 degree Water contact angle) only carry out the water contact angle measurement of round-trip 2 Wan Cihou of number.
Embodiment 28-2
In addition to by hard conating formation coating with other than being combined into and changing as shown in table 2, whole and embodiment 1 is same, carries out the production transitivity evaluation of resin multilayer body.Show the result in table 6.
Embodiment 34
As transparent resin sheet, above-mentioned a2-1 is used instead of above-mentioned a1-1, in addition to this all similarly to Example 20, Carry out the production transitivity evaluation of transparent resin lamilate.Show the result in table 8.
Embodiment 35
As transparent resin sheet, above-mentioned a3-1 is used instead of above-mentioned a1-1, in addition to this all similarly to Example 20, Carry out the production transitivity evaluation of transparent resin lamilate.Show the result in table 8.
Embodiment 36
As transparent resin sheet, above-mentioned a4-1 is used instead of above-mentioned a1-1, in addition to this all similarly to Example 20, Carry out the production transitivity evaluation of transparent resin lamilate.Show the result in table 8.
Embodiment 37
As transparent resin sheet, above-mentioned a5-1 is used instead of above-mentioned a1-1, in addition to this all similarly to Example 20, Carry out the production transitivity evaluation of transparent resin lamilate.Show the result in table 8.
Table 5
Table 6
Table 7
Table 8
The suitable physical property of the material of transparent resin lamilate performance of the invention as substitution glass.In addition, as transparent Resin sheet used the embodiment 20-33 of poly- (methyl) acrylimide series resin sheet, 37 transparent resin lamilate it is transparent Property is especially excellent.On the other hand, the resistance to wiping of the transparent resin lamilate of the comparative example 1 without ingredient C is poor.Ingredient C is more than The hue difference of the transparent resin lamilate of the comparative example 2 of specified amount.The transparent resin of the comparative example 3 of ingredient B deficiency specified amount The resistance to wiping of lamilate is poor.The transparent resin lamilate that ingredient B ultrasound crosses the comparative example 4 of specified amount is difficult to show hydrophobicity.Generation Having used for ingredient B has alkoxysilyl and epoxy group, does not have the comparative example 5 of the compound of (methyl) acryloyl group Transparent resin lamilate resistance to wiping it is poor.Having used instead of ingredient B has alkoxysilyl and amino, does not have The hue difference of the transparent resin lamilate of the comparative example 6 of the compound of (methyl) acryloyl group.It has been used four just instead of ingredient C The resistance to wiping of the transparent resin lamilate of the comparative example 7 of propoxyl group zirconium is poor.
Industrial applicability
It is formed with the coating by the active energy line curing resin composition containing the above-mentioned first aspect of the present invention Hard conating hard conating laminate film due to above-mentioned many excellents, preferably be used as liquid crystal display, plasma The component of the image display devices such as display, electroluminescent display is (including the image display device with touch panel function And the not no image display device of touch panel function), the display pannel of especially touch panel properly uses.
In addition, the transparent resin lamilate of above-mentioned second aspect of the invention is due to above-mentioned many excellents, it can Surface as families' electrical article such as the window or windshield of vehicle, the window of building or door, the protection board of electronic signs, refrigerator The component of the door and show window of the furniture such as component, kitchen cabinet etc. is preferably used.
Symbol description
1: extruder 1
2: extruder 2
The coextrusion T die head of 3 layers of branch manifold mode of 3:2 kind
4: fused film
5: mirror roller
6: mirror surface band
7: a pair of of belt roller
8:T die head
9: molten sheet
10: mirror roller
11: mirror surface band
12: a pair of of belt roller

Claims (27)

1. active energy line curing resin composition contains
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts,
Wherein the organic titanium is selected from least one of the following: tetraisopropoxy titanium, four titanium n-butoxides, four (2- ethyl hexyls Oxygroup) titanium, isopropoxy octamethylene glycolic titanium, bis- (levulinic ketone group) titaniums of diisopropoxy, the two bis- (second of oxygroup titanium of propane Ethyl acetoacetic acid ethyl ester), tri-n-butoxytitanium monostearate, diisopropoxy titanium distearate, titanium stearate, diisopropoxy Titanium diisopstearate, (2- n-butoxycarbonyl benzoyloxy) three titanium butoxides, two n-butoxies-bis- (triethanolamine) Titanium；And their a kind or more the polymer constituted；And
(D) the particle 5-100 mass parts of average grain diameter 1-300nm.
2. active energy line curing resin composition according to claim 1, wherein the organic titanium of component (C) includes four At least one in titanium isopropoxide, four titanium n-butoxides, four (2- ethyl hexyl oxy) titaniums and isopropoxy octamethylene glycolic titanium Kind.
3. active energy line curing resin composition according to claim 1 further contains (E) hydrophobing agent 0.01-7 mass parts.
4. active energy line curing resin composition according to claim 3, wherein above-mentioned (E) hydrophobing agent contains The perfluoroalkyl polyether system hydrophobing agent of (methyl) acryloyl group.
5. hard conating laminate film, it includes transparent resin films, and the transparent resin film at least single side by contain with good grounds power The hard conating that benefit requires the coating of active energy line curing resin composition described in any one of 1-4 to be formed.
6. hard conating laminate film has the first hard conating in order since most surface layer side；Transparent resin film layer；And second is hard Coating, wherein above-mentioned first hard conating is as containing active energy ray-curable tree described according to claim 1 any one of -4 The coating of oil/fat composition is formed.
7. hard conating laminate film according to claim 5, wherein above-mentioned transparent resin film is poly- (methyl) acrylimide Resin film.
8. hard conating laminate film according to claim 6, wherein above-mentioned transparent resin film is poly- (methyl) acrylimide Resin film.
9. hard conating laminate film according to claim 7, wherein above-mentioned poly- (methyl) acrylimide resin film be by Sequence is directly laminated the first poly- (methyl) acrylimide resin (α 1)；Aromatic polycarbonate resin (β)；And the The transparent multilayer film of dimerization (methyl) acrylimide resin (α 2).
10. hard conating laminate film according to claim 8, wherein above-mentioned poly- (methyl) acrylimide resin film be by Sequence is directly laminated the first poly- (methyl) acrylimide resin (α 1)；Aromatic polycarbonate resin (β)；And the The transparent multilayer film of dimerization (methyl) acrylimide resin (α 2).
11. touch panel display panel hard conating laminate film, it includes transparent resin films, and the transparent resin film extremely Few single side has the hard conating formed by the coating containing active energy line curing resin composition, and the hard conating laminate film is full Foot states the important document of (1-i)-(1-v):
(1-i) complete 80% or more light transmittance；
3.0% or less (1-ii) mist degree；
3 or less (1-iii) yellow index；
100 degree of water contact angle or more of (1-iv) touch surface；And
After (1-v) touch panel 20,000 times round-trip gauze wipings, 100 degree of water contact angle or more of touch surface.
12. touch panel display panel hard conating laminate film, it includes transparent resin films, and the transparent resin film extremely Few single side has the hard conating formed by the coating containing active energy line curing resin composition,
Wherein the active energy line curing resin composition contains:
(A) multifunctional (methyl) acrylate；
(B) with the compound of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium,
Wherein the organic titanium is selected from least one of the following: tetraisopropoxy titanium, four titanium n-butoxides, four (2- ethyl hexyls Oxygroup) titanium, isopropoxy octamethylene glycolic titanium, bis- (levulinic ketone group) titaniums of diisopropoxy, the two bis- (second of oxygroup titanium of propane Ethyl acetoacetic acid ethyl ester), tri-n-butoxytitanium monostearate, diisopropoxy titanium distearate, titanium stearate, diisopropoxy Titanium diisopstearate, (2- n-butoxycarbonyl benzoyloxy) three titanium butoxides, two n-butoxies-bis- (triethanolamine) Titanium；And their a kind or more the polymer constituted；And
(D) particle of average grain diameter 1-300nm；And
Wherein the laminate film meets the important document of following (1-i)-(1-v):
(1-i) complete 80% or more light transmittance；
3.0% or less (1-ii) mist degree；
3 or less (1-iii) yellow index；
100 degree of water contact angle or more of (1-iv) touch surface；And
After (1-v) touch panel 20,000 times round-trip gauze wipings, 100 degree of water contact angle or more of touch surface.
13. the manufacturing method of hard conating laminate film according to claim 11 or 12 comprising following process: will contain Have
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts；And
(D) the hard conating shape of the active energy line curing resin composition of the particle 5-100 mass parts of average grain diameter 1-300nm At at least single side for being coated on poly- (methyl) acrylimide resin film with coating, the process for forming hard conating.
14. the manufacturing method of hard conating laminate film according to claim 11 or 12 comprising following process: will contain Have
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts；
(D) the particle 5-100 mass parts of average grain diameter 1-300nm；And
(E) the hard conating formation of the active energy line curing resin composition of hydrophobing agent 0.01-7 mass parts is coated on coating At least single side of poly- (methyl) acrylimide resin film, the process for forming hard conating.
15. according to the method for claim 14, wherein above-mentioned (E) hydrophobing agent includes that the fluorine containing (methyl) acryloyl group is poly- Ether system hydrophobing agent.
16. image display device component contains hard conating laminate film according to claim 5.
17. image display device component contains hard conating laminate film according to claim 6.
18. image display device component contains hard conating laminate film according to claim 11 or 12.
19. transparent resin lamilate has the layer of hard conating and the layer of transparent resin sheet in order since most surface layer side,
Above-mentioned hard conating is by containing
(A) 100 mass parts of multifunctional (methyl) acrylate；
(B) with the compound 0.2-4 mass parts of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium 0.05-3 mass parts,
Wherein the organic titanium is selected from least one of the following: tetraisopropoxy titanium, four titanium n-butoxides, four (2- ethyl hexyls Oxygroup) titanium, isopropoxy octamethylene glycolic titanium, bis- (levulinic ketone group) titaniums of diisopropoxy, the two bis- (second of oxygroup titanium of propane Ethyl acetoacetic acid ethyl ester), tri-n-butoxytitanium monostearate, diisopropoxy titanium distearate, titanium stearate, diisopropoxy Titanium diisopstearate, (2- n-butoxycarbonyl benzoyloxy) three titanium butoxides, two n-butoxies-bis- (triethanolamine) Titanium；And their a kind or more the polymer constituted；And
(D) coating of the particle 5-100 mass parts of average grain diameter 1-300nm is formed.
20. transparent resin lamilate according to claim 19, wherein the organic titanium of component (C) includes tetraisopropoxide At least one of titanium, four titanium n-butoxides, four (2- ethyl hexyl oxy) titaniums and isopropoxy octamethylene glycolic titanium.
21. transparent resin lamilate described in 9 or 20 according to claim 1, wherein above-mentioned hard conating is dredged by further containing (E) The coating of aqua 0.01-7 mass parts is formed.
22. transparent resin lamilate according to claim 21, wherein above-mentioned transparent resin sheet is poly- (methyl) acryloyl Imines series resin sheet.
23. transparent resin lamilate described in 9 or 20 according to claim 1, wherein above-mentioned transparent resin sheet is poly- (methyl) third Alkene imide series resin sheet.
24. transparent resin lamilate according to claim 23, wherein above-mentioned poly- (methyl) acrylimide series resin sheet It has been directly laminated first poly- (methyl) acrylimide resin in order；Aromatic polycarbonate resin；And second The laminated sheet of poly- (methyl) acrylimide resin.
25. transparent resin lamilate, it is characterised in that it has the layer of hard conating and poly- (first in order since most surface layer side Base) acrylimide series resin sheet layer, which meets following characteristics (2-i)-(2-iii):
(2-i) complete 80% or more light transmittance；
5% or less (2-ii) mist degree；And
3 or less (2-iii) yellow index.
26. transparent resin lamilate, it is characterised in that it has the layer of hard conating and poly- (first in order since most surface layer side Base) acrylimide series resin sheet layer, wherein the hard conating is by forming containing coating below:
(A) multifunctional (methyl) acrylate；
(B) with the compound of alkoxysilyl and (methyl) acryloyl group；
(C) organic titanium,
Wherein the organic titanium is selected from least one of the following: tetraisopropoxy titanium, four titanium n-butoxides, four (2- ethyl hexyls Oxygroup) titanium, isopropoxy octamethylene glycolic titanium, bis- (levulinic ketone group) titaniums of diisopropoxy, the two bis- (second of oxygroup titanium of propane Ethyl acetoacetic acid ethyl ester), tri-n-butoxytitanium monostearate, diisopropoxy titanium distearate, titanium stearate, diisopropoxy Titanium diisopstearate, (2- n-butoxycarbonyl benzoyloxy) three titanium butoxides, two n-butoxies-bis- (triethanolamine) Titanium；And their a kind or more the polymer constituted；And
(D) particle of average grain diameter 1-300nm；And
Wherein the transparent resin lamilate meets following characteristics (2-i)-(2-v):
(2-i) complete 80% or more light transmittance；
5% or less (2-ii) mist degree；And
3 or less (2-iii) yellow index.
100 degree of water contact angle or more of (2-iv) touch surface；And
After (2-v) hard coating surface 20,000 times round-trip gauze wipings, 100 degree of water contact angle or more of touch surface.
27. vehicle component or building member contain transparent described in any one of 9,20,25 or 26 according to claim 1 Resin multilayer body.
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